Pesticidally active heterocyclic derivatives with sulphur and hydroxylamine substituents

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides and can be prepared in a manner known per se.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage application of InternationalApplication No. PCT/EP2017/074590, filed Sep. 28, 2017, which claimspriority to European Application No. 201611036908 filed Oct. 27, 2016,the entire contents of which applications are hereby incorporated byreference.

The present invention relates to pesticidally active, in particularinsecticidally active heterocyclic derivatives containing sulphursubstituents, to compositions comprising those compounds, and to theiruse for controlling animal pests (including arthropods and in particularinsects or representatives of the order Acarina).

Heterocyclic compounds with pesticidal action are known and described,for example, in WO 2012/086848, WO 2013/018928 and WO 2016/023954.

There have now been found novel pesticidally active heterocyclicderivatives with sulphur containing phenyl and pyridyl substituents.

The present invention accordingly relates to compounds of formula I,

whereinA is CH or N;X is S, SO, SO₂ or SO(NH);R₁ is C₁-C₆alkyl, C₁-C₆ haloalkyl, C₁-C₄alkyl-C₃-C₆cycloalkyl,C₃-C₆halocycloalkyl, C₁-C₄alkyl-C₃-C₆halocycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl or C₂-C₆ haloalkynyl; orR₁ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄haloalkyl and C₁-C₄alkyl;R₂ is cyano, C₁-C₆haloalkyl, C₁-C₆haloalkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; orR₂ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄haloalkyl, C₁-C₄alkoxy and C₁-C₄alkyl;R₄ is hydrogen, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl or C₂-C₆ haloalkynyl; orR₄ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄haloalkyl, C₁-C₄alkoxy and C₁-C₄alkyl; orR₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano, C₃-C₆cycloalkyl, phenyl,pyridyl, pyrimidinyl, C₁-C₄ alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy;R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, R₇R₈N—, hydroxyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, —SF₅ or—N═S(O)_(p)R₉R₁₀; orR₃ and R₆ are independently C₃-C₆cycloalkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, C₁-C₄alkyl, C₁-C₄haloalkyl, cyano and C₁-C₄alkoxy; orR₃ and R₆ are independently C₁-C₄alkyl-C₃-C₆cycloalkyl which can bemono- or polysubstituted by substituents selected from the groupconsisting of halogen, C₁-C₄alkyl, C₁-C₄haloalkyl and cyano; orR₃ and R₆ are independently C₁-C₄alkyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylsulfanyl,C₁-C₄haloalkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfonyl, R₇R₈N— and hydroxyl; orR₃ and R₆ are independently a five- to six-membered aromatic ringsystem, linked via a carbon atom to the ring which contains thesubstituent A, said ring system can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,nitro, C₁-C₄alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆haloalkynyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, R₇R₈N—, hydroxyl and —C(O)C₁-C₄haloalkyl; andsaid ring system can contain 1, 2 or 3 heteroatoms selected from thegroup consisting of nitrogen, oxygen and sulphur, where said ring systemmay not contain more than one oxygen atom and not more than one sulfuratom; orR₃ and R₆ are independently a five-membered aromatic ring system linkedvia a nitrogen atom to the ring which contains the substituent A, saidring system can be mono- or polysubstituted by substituents selectedfrom the group consisting of halogen, cyano, nitro, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, R₇R₈N—, hydroxyl and —C(O)C₁-C₄haloalkyl; andsaid ring system contains 1, 2 or 3 heteroatoms selected from the groupconsisting of nitrogen, oxygen and sulphur, where said ring system maynot contain more than one oxygen atom and not more than one sulfur atom;R₅ is C₁-C₆alkyl; orR₅ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano, C₁-C₄ alkylsulfanyl,C₁-C₄haloalkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy;R₇ and R₈ are independently hydrogen, cyano, C₂-C₄ alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₂-C₄haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, —C(O)C₁-C₄haloalkyl; orR₇ and R₈ are independently —C(O)C₃-C₆cycloalkyl wherein theC₃-C₆cycloalkyl can be mono- to polysubstituted by substituents selectedfrom the group consisting of halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkyl; orR₇ and R₈ are independently C₃-C₆cycloalkyl which can be mono- topolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄ haloalkyl and C₁-C₄alkyl;R₉ and R₁₀ are independently C₁-C₄alkyl or C₁-C₄haloalkyl; orR₉ and R₁₀ are independently C₃-C₆cycloalkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄ haloalkyl and C₀-C₄alkyl; andp is 0 or 1;and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, a phosphorus acid or a hydrohalic acid, with strong organiccarboxylic acids, such as C₁-C₄alkanecarboxylic acids which areunsubstituted or substituted, for example by halogen, for example aceticacid, such as saturated or unsaturated dicarboxylic acids, for exampleoxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid orphthalic acid, such as hydroxycarboxylic acids, for example ascorbicacid, lactic acid, malic acid, tartaric acid or citric acid, or such asbenzoic acid, or with organic sulfonic acids, such as C₁-C₄alkane- orarylsulfonic acids which are unsubstituted or substituted, for exampleby halogen, for example methane- or p-toluenesulfonic acid. Compounds offormula I which have at least one acidic group can form, for example,salts with bases, for example mineral salts such as alkali metal oralkaline earth metal salts, for example sodium, potassium or magnesiumsalts, or salts with ammonia or an organic amine, such as morpholine,piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, forexample ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-,di- or trihydroxy-lower-alkylamine, for example mono-, di- ortriethanolamine.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl,hexyl, nonyl, decyl and their branched isomers. Alkylsulfanyl,alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals arederived from the alkyl radicals mentioned. The alkenyl and alkynylgroups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also theisomeric pentyloxy and hexyloxy radicals.

Haloalkoxy groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy or2,2,2-trifluoroethoxy.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atomscontaining one or more oxygen atoms. Alkoxyalkyl is, for example,methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl,n-propoxyethyl, isopropoxymethyl, isopropoxyethyl or a dialkoxyalkylderivative such as for example —CH₂OCH₂CH₂OCH₃.

Alkoxycarbonyl is for example methoxycarbonyl (which isCialkoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl orhexoxycarbonyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

In the context of this invention “mono- to polysubstituted” in thedefinition of the substituents, means typically, depending on thechemical structure of the substituents, monosubstituted to seven-timessubstituted, preferably monosubstituted to five-times substituted, morepreferably mono-, di- or tri-substituted.

As used herein, the term “C₂-C₆alkynyl” refers to a straight or branchedhydrocarbon chain radical group consisting solely of carbon and hydrogenatoms, containing at least one triple bond, having from two to sixcarbon atoms, and which is attached to the rest of the molecule by asingle bond. The term “C₂-C₄alkynyl” and “C₂-C₃alkynyl” are to beconstrued accordingly. Examples of C₂-C₆ alkynyl include, but are notlimited to, ethynyl, prop-1-ynyl, but-1-ynyl and but-2-ynyl.

As used herein, the term “C₂-C₆alkenyl” refers to a straight or branchedhydrocarbon chain radical group consisting solely of carbon and hydrogenatoms, containing at least one double bond, having from two to sixcarbon atoms, and which is attached to the rest of the molecule by asingle bond. The term “C₂-C₄alkenyl” and “C₂-C₃alkenyl” are to bedefined accordingly. Examples of C₂-C₆alkenyl include, but are notlimited to prop-1-enyl, but-1-enyl and but-2-enyl.

Alkylsulfanyl is for example methylsulfanyl, ethylsulfanyl,propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl andhexylsulfanyl.

Alkylsulfinyl is for example methylsulfinyl, ethylsulfinyl,propylsulfinyl, isopropylsulfinyl, a butylsulfinyl, pentylsulfinyl orhexylsulfinyl.

Alkylsulfonyl is for example methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl orhexylsulfonyl.

Haloalkylsulfanyl is for example difluoromethylsulfanyl,trifluoromethylsulfanyl, 2, 2,2-trifluoroethylsulfanyl orpentafluoroethylsulfanyl.

Haloalkylsulfinyl is for example difluoromethylsulfinyl,trifluoromethylsulfinyl, 2, 2,2-trifluoroethylsulfinyl orpentafluoroethylsulfinyl.

Haloalkylsulfonyl is for example difluoromethylsulfonyl,trifluoromethylsulfonyl, 2, 2,2-trifluoroethylsulfonyl orpentafluoroethylsulfonyl.

In the context of this invention, examples of “five-membered aromaticring system linked via a nitrogen atom to the ring which contains thesubstituent A” are, but are not limited to, pyrazolyl, imidazolyl,pyrrolyl, triazolyl and tetrazolyl. If said five-membered aromatic ringsystem contains more than one nitrogen atom, then it may be linked viaany nitrogen atom to the ring which contains the substituent A.

In the context of this invention, examples of “five- to six-memberedaromatic ring system, linked via a carbon atom to the ring whichcontains the substituent A” are, but are not limited to, phenyl,pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, isoxazolyl, furanyl, thienyl,imidazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl,thiadiazolyl, tetrazolyl, furyl, pyrazinyl, pyridazinyl and triazinyl.Said five- to six-membered aromatic ring system may be linked via anycarbon atom to the ring which contains the substituent A.

The compounds of formula I according to the invention also includehydrates which may be formed during the salt formation.

Free radicals represents methyl groups.

Preferred are compounds of formula I,

wherein

A is CH or N;

X is S, SO or SO₂;

R₁ is C₁-C₆alkyl;

R₂ is C₁-C₆haloalkyl, C₁-C₆haloalkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

R₄ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl or C₂-C₆haloalkynyl; or

R₄ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄haloalkyl and C₁-C₄alkyl; or

R₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of cyano, C₃-C₆cycloalkyl, phenyl, pyridine,pyrimidine, C₁-C₄alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy;R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆ alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, R₇R₈N—, hydroxyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, —SF5 or—N═S(O)_(p)R₉R₁₀; orR₃ and R₆ are independently C₃-C₆cycloalkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, C₁-C₄alkyl, C₁-C₄haloalkyl and cyano; orR₃ and R₆ are independently C₁-C₄alkyl-C₃-C₆cycloalkyl which can bemono- or polysubstituted by substituents selected from the groupconsisting of halogen, C₁-C₄alkyl, C₁-C₄haloalkyl and cyano; orR₃ and R₆ are C₁-C₄alkyl mono- or polysubstituted by substistuentsselected from the group consisting of cyano, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄ alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl, R₇R₈N— and hydroxyl; orR₃ and R₆ are independently phenyl, pyridyl or pyrimidyl, all linked viaa carbon atom to the ring which contains the substituent A, said phenyl,pyridyl or pyrimidyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, nitro,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, R₇R₈N-hydroxyl and —C(O)C₁-C₄haloalkyl; orR₃ and R₆ are independently triazolyl or pyrazolyl, both linked via anitrogen atom to the ring which contains the substituent A, saidtriazolyl or pyrazolyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, nitro,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,C₁-C₄alkoxy C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, R₇R₈N-hydroxyl and —C(O)C₁-C₄haloalkyl;R₅ is C₁-C₆alkyl;R₇ and R₈ are independently hydrogen, cyano, C₂-C₄ alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₂-C₄haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆cycloalkyl, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or —C(O)C₁-C₄haloalkyl;orR₇ and R₈ are independently —C(O)C₃-C₆cycloalkyl wherein theC₃-C₆cycloalkyl group can be mono- to polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkyl;R₉ and R₁₀ are independently C₁-C₄alkyl or C₁-C₄haloalkyl; orR₉ and R₁₀ are independently C₃-C₆cycloalkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄haloalkyl and C₁-C₄alkyl; andp is 0 or 1.

Further preferred are compounds of formula I,

wherein

A is CH or N;

X is S, SO or SO₂;

R₁ is C₁-C₆alkyl;

R₂ is C₁-C₆haloalkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl;

R₄ is hydrogen, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl or C₂-C₆haloalkynyl; or

R₄ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄haloalkyl and C₁-C₄alkyl; or

R₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of cyano, C₃-C₆cycloalkyl, phenyl, pyridyl,pyrimidinyl, C₁-C₄alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy;R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylsulfanyl,C₁-C₆haloalkylsulfanyl, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, R₇R₈N— or —N═S(O)_(p)R₉R₁₀;orR₃ and R₆ are independently C₃-C₆cycloalkyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, C₁-C₄alkyl, C₁-C₄haloalkyl and cyano; orR₃ and R₆ are C₁-C₄alkyl mono- or polysubstituted by substituentsselected from the group consisting of cyano, C₁-C₄alkoxy,C₁-C₄haloalkoxy, C₁-C₄ alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl, R₇R₈N— and hydroxyl; orR₃ and R₆ are independently phenyl, pyridyl or pyrimidyl, all linked viaa carbon atom to the ring which contains the substituent A, said phenyl,pyridyl or pyrimidyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkoxyC₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₁-C₄alkyl-C₃-C₆cycloalkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, R₇R₈N— and hydroxyl; orR₃ and R₆ are independently triazolyl or pyrazolyl, both linked via anitrogen atom to the ring which contains the substituent A, saidtriazolyl or pyrazolyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,R₇R₈N— and hydroxyl;R₅ is C₁-C₆alkyl;R₇ and R₈ are independently hydrogen, cyano, C₁-C₄alkyl, cyclopropyl,C₁-C₄haloalkyl or C₁-C₄alkoxy;orR₇ and R₈ are independently —C(O)cyclopropyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄haloalkyl and C₁-C₄alkyl;R₉ and R₁₀ are independently C₁-C₄alkyl or C₁-C₄haloalkyl; orR₉ and R₁₀ are independently cyclopropyl which can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄haloalkyl and C₁-C₄alkyl; andp is 0 or 1.

Further preferred are compounds of formula I,

wherein

A is CH or N;

X is S, SO or SO₂;

R₁ is C₁-C₄alkyl;

R₂ is C₁-C₄haloalkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl orC₁-C₄haloalkylsulfonyl;

R₄ is hydrogen, C₁-C₆alkyl or C₁-C₆ haloalkyl; or

R₄ is cyclopropyl which can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄ haloalkyland C₀-C₄alkyl; or

R₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of cyano, cyclopropyl, phenyl, pyridyl,pyrimidinyl, C₁-C₄alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy;R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or R₇R₈N—; orR₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; orR₃ and R₆ are independently C₁-C₄alkyl which can be monosubstituted bycyano; orR₃ and R₆ are independently phenyl, pyridyl or pyrimidyl, all linked viaa carbon atom to the ring which contains the substituent A, said phenyl,pyridyl or pyrimidyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,R₇R₈N— and hydroxyl; orR₃ and R₆ are independently triazolyl or pyrazolyl, both linked via anitrogen atom to the ring which contains the substituent A, saidtriazolyl or pyrazolyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,R₇R₈N— and hydroxyl;R₅ is C₁-C₆alkyl; andR₇ and R₈ are independently hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl,cyclopropyl, —C(O)cyclopropyl or C₁-C₄alkoxy.

Even further preferred are compounds of formula I,

wherein

A is CH or N;

X is S, SO or SO₂;

R₁ is C₁-C₄alkyl;

R₂ is C₁-C₄haloalkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl orC₁-C₄haloalkylsulfonyl;

R₄ is hydrogen or C₁-C₆alkyl;

R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or R₇R₈N—; or

R₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently C₁-C₄alkyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently phenyl, pyridyl or pyrimidyl, all linked viaa carbon atom to the ring which contains the substituent A, said phenyl,pyridyl or pyrimidyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,R₇R₈N— and hydroxyl; orR₃ and R₆ are independently triazolyl or pyrazolyl, both linked via anitrogen atom to the ring which contains the substituent A, saidtriazolyl or pyrazolyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,R₇R₈N— and hydroxyl;R₅ is C₁-C₆alkyl; andR₇ and R₈ are independently hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl,cyclopropyl, —C(O)cyclopropyl or C₁-C₄alkoxy.

Even further preferred are compounds of formula I,

wherein

A is CH or N;

X is S, SO or SO₂;

R₁ is C₁-C₄alkyl;

R₂ is C₁-C₄haloalkyl;

R₄ is hydrogen or C₁-C₆alkyl;

R₃ and R₆ are independently hydrogen, halogen, C₁-C₆haloalkyl or R₇R₈N—;or

R₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently C₁-C₄alkyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently triazolyl, linked via any nitrogen atom tothe ring which contains the substituent A, said triazolyl can bemonosubstituted by substituents selected from the group consisting ofhalogen and cyano;

R₅ is C₁-C₆alkyl; and

R₇ and R₈ are independently hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl,cyclopropyl, —C(O)cyclopropyl or C₁-C₄alkoxy.

Especially preferred are compounds of formula I,

wherein

A is CH or N;

X is S, SO or SO₂, preferably S or SO₂;

R₁ is C₁-C₄alkyl, preferably methyl or ethyl;

R₂ is C₁-C₄haloalkyl, preferably trifluoromethyl;

R₄ is hydrogen or C₁-C₆alkyl, preferably hydrogen, methyl or ethyl, morepreferably methyl;

R₃ and R₆ are independently hydrogen, halogen, C₁-C₆haloalkyl or R₇R₈N—;or

R₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently C₁-C₄alkyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently unsubstituted triazolyl, linked via anynitrogen atom to the ring which contains the substituent A;

R₅ is C₁-C₆alkyl, preferably methyl; and

R₇ and R₈ are independently hydrogen or C₁-C₄alkyl, preferably hydrogenor methyl, more preferably hydrogen;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of said especially preferred are compounds offormula I.

Further preferred are compounds of formula I represented by thecompounds of formula I-10,

whereinA is CH or N;X is S, SO or SO₂;R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy or R₇R₈N—;R₄ is hydrogen, C₁-C₆alkyl or C₁-C₆haloalkyl; orR₄ is cyclopropyl which can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkyl; orR₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of cyano, cyclopropyl, phenyl, pyridyl,pyrimidinyl, C₁-C₄ alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy;R₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; orR₃ and R₆ are independently phenyl, pyridyl or pyrimidyl, all linked viaa carbon atom to the ring which contains the substituent A, said phenyl,pyridyl or pyrimidyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,R₇R₈N— and hydroxyl; orR₃ and R₆ are independently triazolyl or pyrazolyl, both linked via anitrogen atom to the ring which contains the substituent A, saidtriazolyl or pyrazolyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkoxyC₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₁-C₄alkyl-C₃-C₆cycloalkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, R₇R₈N— and hydroxyl; andR₇ and R₈ are independently hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl,cyclopropyl, —C(O)cyclopropyl or C₁-C₄alkoxy.

Further preferred are compounds of formula I-10, wherein

A is CH or N;

X is S, SO or SO₂;

R₄ is hydrogen, C₁-C₆alkyl or C₁-C₆haloalkyl;

R₃ and R₆ are independently hydrogen, halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄alkoxy or R₇R₈N—; or

R₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; or

R₃ and R₆ are independently phenyl, pyridyl or pyrimidyl, all linked viaa carbon atom to the ring which contains the substituent A, said phenyl,pyridyl or pyrimidyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkoxyC₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₁-C₄alkyl C₃-C₆cycloalkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl and C₁-C₄haloalkylsulfonyl; orR₃ and R₆ are independently triazolyl or pyrazolyl, both linked via anitrogen atom to the ring which contains the substituent A, saidtriazolyl or pyrazolyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl andC₁-C₄haloalkylsulfonyl; andR₇ and R₈ are independently hydrogen, C₁-C₄alkyl, —C(O)cyclopropyl orcyclopropyl.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-1

wherein the substituents X, R₁, R₂, R₃, R₆, R₄ and A are as definedunder formula I above.

Further preferred embodiments of the invention are:

EMBODIMENT (A1)

Preferred are compounds of formula I-1, wherein

R₁ is C₁-C₆alkyl or C₁-C₄alkyl-C₃-C₆cycloalkyl;

R₂ is cyano, C₁-C₆haloalkyl, C₁-C₆haloalkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; or

R₂ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano orC₁-C₄haloalkyl;

R₄ is hydrogen, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆alkenyl orC₂-C₆alkynyl; or

R₄ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano orC₁-C₄haloalkyl; or

R₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano, C₃-C₆cycloalkyl, phenyl,pyridyl, C₁-C₄ alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₁-C₄alkoxy; andX, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A2)

Preferred are compounds of formula I-1, wherein

R₁ is C₁-C₆alkyl;

R₂ is C₁-C₆haloalkyl, C₁-C₆haloalkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

R₄ is hydrogen or C₁-C₆alkyl; and

X, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A3)

Preferred are compounds of formula I-1, wherein

R₁ is C₁-C₆alkyl;

R₂ is C₁-C₆haloalkyl;

R₄ is hydrogen or C₁-C₆alkyl; and

X, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A4)

In compounds of formula I-1 and all of the preferred embodiments ofcompounds of formula I-1 mentioned above, A is N or CH, X is preferablyS or SO₂, and

R₃ and R₆ preferably are independently hydrogen, halogen, C₁-C₆haloalkylor R₇R₈N—; or

R₃ and R₆ preferably are independently cyclopropyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently C₁-C₄alkyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently triazolyl or pyrazolyl, whicheach can be mono-substituted by substituents selected from the groupconsisting of halogen and cyano; wherein

R₇ and R₈ are hydrogen.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-2

wherein the substituents X, R₁, R₃, R₆, R₄ and A are as defined underformula I above.

Further preferred embodiments of the invention are:

EMBODIMENT (A5)

Preferred are compounds of formula I-2, wherein

R₁ is C₁-C₆alkyl or C₁-C₄alkyl-C₃-C₆cycloalkyl;

R₄ is hydrogen, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆alkenyl orC₂-C₆alkynyl; or

R₄ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano orC₀-C₄haloalkyl; or

R₄ is C₁-C₄alkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano, C₃-C₆cycloalkyl, phenyl,pyridyl, C₁-C₄ alkylsulfanyl, C₁-C₄haloalkylsulfanyl,C₁-C₄alkylsulfinyl, C₀-C₄haloalkylsulfinyl, C₁-C₄alkylsulfonyl,C₁-C₄haloalkylsulfonyl and C₀-C₄alkoxy; andX, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A6)

Preferred are compounds of formula I-2, wherein

R₁ is C₁-C₆alkyl;

R₄ is hydrogen or C₁-C₆alkyl; and

X, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A7)

In compounds of formula I-2 and all of the preferred embodiments ofcompounds of formula I-2 mentioned above, A is N or CH, X is preferablyS or SO₂, and

R₃ and R₆ preferably are independently hydrogen, halogen, C₁-C₆haloalkylor R₇R₈N—; or

R₃ and R₆ preferably are independently cyclopropyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently C₁-C₄alkyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently triazolyl or pyrazolyl, whicheach can be mono-substituted by substituents selected from the groupconsisting of halogen and cyano; wherein

R₇ and R₈ are hydrogen.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-3

wherein the substituents X, R₁, R₃, R₆ and A are as defined underformula I above.

Further preferred embodiments of the invention are:

EMBODIMENT (A8)

Preferred are compounds of formula I-3, wherein

R₁ is C₁-C₆alkyl or C₁-C₄alkyl-C₃-C₆cycloalkyl; and

X, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A9)

Preferred are compounds of formula I-3, wherein

R₁ is C₁-C₆alkyl; and

X, R₃, R₆ and A are as defined under formula I above.

EMBODIMENT (A10)

In compounds of formula I-3 and all of the preferred embodiments ofcompounds of formula I-3 mentioned above, A is N or CH, X is preferablyS or SO₂, and

R₃ and R₆ preferably are independently hydrogen, halogen, C₁-C₆haloalkylor R₇R₈N—; or

R₃ and R₆ preferably are independently cyclopropyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently C₁-C₄alkyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently triazolyl or pyrazolyl, whicheach can be mono-substituted by substituents selected from the groupconsisting of halogen and cyano; wherein

R₇ and R₈ are hydrogen.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-4

wherein the substituents X, R₃, R₆ and A are as defined under formula Iabove.

Further preferred embodiments of the invention are:

EMBODIMENT (A11)

Preferred are compounds of formula I-4, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ and R₆ are as defined under formula I above.

EMBODIMENT (A12)

Preferred are compounds of formula I-4, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ and R₆ preferably are independently hydrogen, halogen, C₁-C₆haloalkylor R₇R₈N—; or

R₃ and R₆ preferably are independently cyclopropyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently C₁-C₄alkyl which can bemonosubstituted by cyano; or

R₃ and R₆ preferably are independently triazolyl or pyrazolyl, whicheach can be mono-substituted by substituents selected from the groupconsisting of halogen and cyano; wherein

R₇ and R₈ are hydrogen;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of said especially preferred are compounds offormula I-4.

EMBODIMENT (A13)

Preferred are compounds of formula I-4, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is halogen, preferably chloro or bromo; and

R₆ is R₇R₈N—; wherein

R₇ and R₈ are independently hydrogen, cyano, C₂-C₄ alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₂-C₄haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, —C(O)C₁-C₄haloalkyl; orR₇ and R₈ are independently —C(O)C₃-C₆cycloalkyl wherein theC₃-C₆cycloalkyl can be mono- to polysubstituted by substituents selectedfrom the group consisting of halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkyl; orR₇ and R₈ are independently C₃-C₆cycloalkyl which can be mono- topolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄ haloalkyl and C₁-C₄alkyl.

EMBODIMENT (A14)

Preferred are compounds of formula I-4, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is halogen, preferably chloro or bromo; and

R₆ is R₇R₈N—; wherein R₇ and R₈ are hydrogen;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of said especially preferred are compounds offormula I-4.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-5

wherein the substituents X, R₃ and A are as defined under formula Iabove.

Further preferred embodiments of the invention are:

EMBODIMENT (B1)

Preferred are compounds of formula I-5, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is as defined under formula I above.

EMBODIMENT (B2)

Preferred are compounds of formula I-5, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is hydrogen, halogen or C₁-C₆haloalkyl, preferably hydrogen, chloro,bromo or trifluoromethyl; or

R₃ is cyclopropyl which can be monosubstituted by cyano; or

R₃ is C₁-C₄alkyl which can be monosubstituted by cyano, preferablyisopropyl which can be monosubstituted by cyano; or

R₃ is R₇R₈N—; or

R₃ is a five-membered aromatic ring system linked via a nitrogen atom tothe ring which contains the substituent A, said ring system can be mono-or polysubstituted by substituents selected from the group consisting ofhalogen, cyano, nitro, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆haloalkynyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, R₇R₈N—, hydroxyl and —C(O)C₁-C₄haloalkyl; andsaid ring system contains 1, 2 or 3 heteroatoms selected from the groupconsisting of nitrogen, oxygen and sulphur, where said ring system maynot contain more than one oxygen atom and not more than one sulfur atom;andR₇ and R₈ are independently hydrogen, cyano, C₂-C₄ alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₂-C₄haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, —C(O)C₁-C₄haloalkyl; orR₇ and R₈ are independently —C(O)C₃-C₆cycloalkyl wherein theC₃-C₆cycloalkyl can be mono- to polysubstituted by substituents selectedfrom the group consisting of halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkyl; orR₇ and R₈ are independently C₃-C₆cycloalkyl which can be mono- topolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄ haloalkyl and C₁-C₄alkyl.

EMBODIMENT (B3)

Preferred are compounds of formula I-5, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is hydrogen, halogen or C₁-C₆haloalkyl, preferably hydrogen, chloro,bromo or trifluoromethyl; or

R₃ is cyclopropyl which can be monosubstituted by cyano; or

R₃ is C₁-C₄alkyl which can be monosubstituted by cyano, preferablyisopropyl which can be monosubstituted by cyano; or

R₃ is R₇R₈N—, wherein R₇ and R₈ are hydrogen; or

R₃ is triazolyl or pyrazolyl, which each can be mono-substituted bysubstituents selected from the group consisting of halogen and cyano.

EMBODIMENT (B4)

Preferred are compounds of formula I-5, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is hydrogen, halogen or C₁-C₆haloalkyl, preferably hydrogen, chloro,bromo or trifluoromethyl; or

R₃ is cyclopropyl which can be monosubstituted by cyano; or

R₃ is C₁-C₄alkyl which can be monosubstituted by cyano, preferablyisopropyl which can be monosubstituted by cyano; or

R₃ is R₇R₈N—, wherein R₇ and R₈ are hydrogen; or

R₃ is unsubstituted triazolyl, linked via any nitrogen atom to the ringwhich contains the substituent A.

EMBODIMENT (B5)

Preferred are compounds of formula I-5, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₃ is hydrogen, halogen or C₁-C₆haloalkyl, preferably hydrogen, chloro,bromo or trifluoromethyl; or

R₃ is cyclopropyl which can be monosubstituted by cyano; or

R₃ is C₁-C₄alkyl which can be monosubstituted by cyano, preferablyisopropyl which can be monosubstituted by cyano;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of said especially preferred are compounds offormula I-5.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-6

wherein the substituents X, R₆ and A are as defined under formula Iabove.

Further preferred embodiments of the invention are:

EMBODIMENT (C1)

Preferred are compounds of formula I-6, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₆ is as defined under formula I above.

EMBODIMENT (C2)

Preferred are compounds of formula I-6, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂;

R₆ is hydrogen, halogen or C₁-C₆haloalkyl, preferably hydrogen, chloro,bromo or trifluoromethyl; or

R₆ is cyclopropyl which can be monosubstituted by cyano; or

R₆ is C₁-C₄alkyl which can be monosubstituted by cyano, preferablyisopropyl which can be monosubstituted by cyano; or

R₆ is R₇R₈N—; or

R₆ is a five-membered aromatic ring system linked via a nitrogen atom tothe ring which contains the substituent A, said ring system can be mono-or polysubstituted by substituents selected from the group consisting ofhalogen, cyano, nitro, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆haloalkynyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkyl-C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, R₇R₈N—, hydroxyl and —C(O)C₁-C₄haloalkyl; andsaid ring system contains 1, 2 or 3 heteroatoms selected from the groupconsisting of nitrogen, oxygen and sulphur, where said ring system maynot contain more than one oxygen atom and not more than one sulfur atom;andR₇ and R₈ are independently hydrogen, cyano, C₂-C₄ alkenyl,C₂-C₄haloalkenyl, C₂-C₄alkynyl, C₂-C₄haloalkynyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, —C(O)C₁-C₄haloalkyl; orR₇ and R₈ are independently —C(O)C₃-C₆cycloalkyl wherein theC₃-C₆cycloalkyl can be mono- to polysubstituted by substituents selectedfrom the group consisting of halogen, cyano, C₁-C₄haloalkyl andC₁-C₄alkyl; orR₇ and R₈ are independently C₃-C₆cycloalkyl which can be mono- topolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄ haloalkyl and C₁-C₄alkyl.

EMBODIMENT (C3)

Preferred are compounds of formula I-6, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₆ is hydrogen, halogen or C₁-C₆haloalkyl, preferably hydrogen, chloro,bromo or trifluoromethyl; or

R₆ is cyclopropyl which can be monosubstituted by cyano; or

R₆ is C₁-C₄alkyl which can be monosubstituted by cyano, preferablyisopropyl which can be monosubstituted by cyano; or

R₆ is R₇R₈N—, wherein R₇ and R₈ are hydrogen; or

R₆ is triazolyl or pyrazolyl, which each can be mono-substituted bysubstituents selected from the group consisting of halogen and cyano.

EMBODIMENT (C4)

Preferred are compounds of formula I-6, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₆ is hydrogen or halogen, preferably hydrogen, fluoro, chloro or bromo;or

R₆ is R₇R₈N—, wherein R₇ and R₈ are hydrogen; or

R₆ is triazolyl or pyrazolyl, which each can be mono-substituted bysubstituents selected from the group consisting of halogen and cyano.

EMBODIMENT (C5)

Preferred are compounds of formula I-6, wherein

A is N or CH;

X is S, SO or SO₂, preferably S or SO₂; and

R₆ is hydrogen or halogen, preferably hydrogen, fluoro, chloro or bromo;or

R₆ is R₇R₈N—, wherein R₇ and R₈ are hydrogen; or

R₆ is unsubstituted triazolyl, linked via any nitrogen atom to the ringwhich contains the substituent A; and agrochemically acceptable salts,stereoisomers, enantiomers, tautomers and N-oxides of said especiallypreferred are compounds of formula I-5.

An especially preferred embodiment of the invention comprises compoundsof formula I represented by the compounds of formula I-7

whereinA is N or CH;X is S or SO₂;R₂ is C₁-C₆haloalkyl, preferably trifluoromethyl;R₄ is C₁-C₆alkyl, preferably methyl; andR₃ and R₆ are independently hydrogen, halogen, C₁-C₆haloalkyl or R₇R₈N—;orR₃ and R₆ are independently cyclopropyl which can be monosubstituted bycyano; orR₃ and R₆ are independently C₁-C₄alkyl which can be monosubstituted bycyano; orR₃ and R₆ are independently unsubstituted triazolyl, linked via anynitrogen atom to the ring which contains the substituent A; whereinR₇ and R₈ are hydrogen;and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of said especially preferred are compounds offormula I-7.

In the especially preferred embodiment of formula I-7 above,

R₃ is preferably hydrogen, halogen or C₁-C₆haloalkyl, in particularhydrogen, chloro, bromo or trifluoromethyl; or

R₃ is preferably cyclopropyl which can be monosubstituted by cyano; or

R₃ is C₁-C₄alkyl which can be monosubstituted by cyano, in particularisopropyl which can be monosubstituted by cyano;

R₆ is preferably hydrogen or halogen, in particular hydrogen, fluoro,chloro or bromo; or

R₆ is preferably R₇R₈N—, wherein R₇ and R₈ are hydrogen; or

R₆ is preferably unsubstituted triazolyl, linked via any nitrogen atomto the ring which contains the substituent A.

The process according to the invention for preparing compounds offormula (I) is carried out by methods known to those skilled in the art,or described for example in WO 2009/131237, WO 2011/043404, WO2011/040629, WO 2010/125985, WO 2012/086848, WO 2013/018928, WO2013/191113, WO 2013/180193, WO 2013/180194, WO 2016/023954 and WO2016/142326, and involves reaction of a compound of formula II,

wherein Q is the group

wherein Z is X—R₁ or a leaving group, for example a halogen (preferablyfluoro or chloro), and wherein X, R₁, R₃, R₆ and A are as describedunder formula I above, and wherein the arrow in the radical Q shows thepoint of attachment to the carbon atom of the carboxyl group in thecompound of formula II, with a compound of formula III,

wherein R₂, R₄ and R₅ are as described under formula I above, in thepresence of a dehydrating agent, such as for example polyphosphoric acidat temperature between 150° C. to 250° C., to yield compounds of formulaIa, wherein the substituents are as described above and under formula I.Such processes are well known and have been described for example in WO2008/128968 or WO 2006/003440. The process is summarized in scheme 1 forcompounds of formula Ia:

As can be seen in scheme 1, the formation of compounds of formula Iaoccurs through the intermediacy of a compound of formula VI (and/or itsposition isomer Via). Intermediate VI or intermediate Via may form as apure entity, or intermediates VI and Via may arise as a mixture ofregioisomeric acylation products. It is in many cases advantageous tothus prepare compounds of formula (I), respectively (Ia), through suchintermediates VI/VIa, which may be isolated and optionally purified.This is illustrated for compounds of formula Ia in scheme 2:

Compounds of the formula VI and/or VIa (or a mixture thereof), or a saltthereof, wherein Q is as defined above, and wherein R₂, R₄ and R₅ are asdescribed under formula I above, may be prepared by

i) activation of compound of formula II, wherein Q is as defined above,by methods known to those skilled in the art and described in, forexample, Tetrahedron, 2005, 61 (46), 10827-10852, to form an activatedspecies IIa, wherein Q is as defined above and wherein X₀₀ is halogen,preferably chlorine. For example, compounds IIa where X₀₀ is halogen,preferably chlorine, are formed by treatment of II with, for example,oxalyl chloride (COCl)₂ or thionyl chloride SOCl₂ in the presence ofcatalytic quantities of N,N-dimethylformamide DMF in inert solvents suchas methylene chloride CH₂Cl₂ or tetrahydrofuran THF at temperaturesbetween 20 to 100° C., preferably 25° C. Alternatively, treatment ofcompounds of formula II with, for example,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC will generate an activated species IIa, wherein X₀₀ isX₀₁ or X₀₂ respectively, in an inert solvent, such as pyridine ortetrahydrofuran THF, optionally in the presence of a base, such astriethylamine, at temperatures between 25-180° C.; followed byii) treatment of the activated species IIa with a compound of formulaIII (or a salt thereof), wherein R₂, R₄ and R₅ are as described underformula I above, optionally in the presence of a base, such astriethylamine or pyridine, in an inert solvents such as dichloromethane,tetrahydrofuran, dioxane or toluene, at temperatures between 0 and 80°C., to form the compounds of formula VI and/or Via (or a mixturethereof).

Compounds of formula VI and/or Via (or a mixture thereof) may further beconverted into compounds of formula Ia, wherein Q is as defined above,and wherein R₂, R₄ and R₅ are as described under formula I above, bydehydration, eg. by heating the compounds VI and/or Via (or a mixturethereof) in the presence of an acid catalyst, such as for examplemethane sulfonic acid, or para-toluene sulfonic acid TsOH, in an inertsolvent such as toluene, xylene, N,N-dimethylfomamide DMF, or N-methylpyrrolidine NMP (or mixtures thereof) at temperatures between 25-180°C., preferably 100-170° C., optionally under microwave conditions.Alternatively, heating the compounds VI and/or Via (or a mixturethereof) in solvents such as acetic acid or trifluoroacetic acid, attemperatures up to the boiling point of the reaction mixture, optionallyunder microwave conditions, will also generate compounds of formula Ia.Such processes have been described previously, for example, in WO2010/125985.

Compounds of formula Ia, wherein Q is as defined above, and wherein Z isa leaving group, for example halogen, preferably fluorine or chlorine,and wherein R₂, R₄ and R₅ are as described under formula I above, can bereacted with compounds of formula VR₁—SH  (V),or a salt thereof, wherein R₁ is as defined in formula I, optionally inthe presence of a suitable base, such as alkali metal carbonates, forexample sodium carbonate and potassium carbonate, or alkali metalhydrides such as sodium hydride, or alkali metal hydroxides such assodium hydroxide and potassium hydroxide, in an inert solvent attemperatures preferably between 25-120° C., to generate compounds offormula Ib, in which X is S (a sulfide), and wherein R₁ is as describedunder formula I above, and in which A, R₂, R₃, R₄, R₅ and R₆ are asdescribed under formula I above. Examples of solvent to be used includeethers such as THF, ethylene glycol dimethyl ether, tert-butylmethylether, and 1,4-dioxane, aromatic hydrocarbons such as toluene andxylene, nitriles such as acetonitrile or polar aprotic solvents such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone ordimethyl sulfoxide. Similar chemistry has been previously described, asfor example in WO 2013/018928. Examples of salts of the compound offormula V include compounds of the formula VaR₁—S-M  (Va),wherein R₁ is as defined above and wherein M is, for example, sodium orpotassium. This is illustrated for compounds of formula Ib in scheme 3:

Alternatively, this reaction can be carried out in the presence of apalladium catalyst, such as tris(dibenzylideneacetone)dipalladium(0), inthe presence of a phosphor ligand, such as xanthphos, in an inertsolvent, for example, xylene at temperatures between 100-160° C.,preferably 140° C., as described by Perrio et al. in Tetrahedron 2005,61, 5253-5259.

The subgroup of compounds of formula I, wherein X is SO (sulfoxide)and/or SO₂ (sulfone), may be obtained by means of an oxidation reactionof the corresponding sulfide compounds of formula I, wherein X is S(i.e. a compound of formula Ib above), involving reagents such as, forexample, m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone,sodium periodate, sodium hypochlorite or tert-butyl hypochlorite amongstother oxidants. The oxidation reaction is generally conducted in thepresence of a solvent. Examples of the solvent to be used in thereaction include aliphatic halogenated hydrocarbons such asdichloromethane and chloroform; alcohols such as methanol and ethanol;acetic acid; water; and mixtures thereof. The amount of the oxidant tobe used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2moles, relative to 1 mole of the sulfide compounds Ib to produce thesulfoxide compounds I (wherein X=SO), and preferably 2 to 2.2 moles ofoxidant, relative to 1 mole of of the sulfide compounds Ib to producethe sulfone compounds I (wherein X═SO₂). Such oxidation reactions aredisclosed, for example, in WO 2013/018928, WO 2016/023954 or WO2016/142326.

The sequence to prepare compounds of formula III wherein R₂, R₄ and R₅are as described under formula I above, from compounds of formula VII,may involve (scheme 4): step i. alkylation of compound VII withR₅—X_(LG), wherein R₅ is as described under formula I above and whereinX_(LG) is a leaving group, such as a halogen, preferably iodine, bromineor chlorine, in presence of a base, such as sodium carbonate, potassiumcarbonate or cesium carbonate, or sodium hydride, in a appropriatesolvent such as for example tetrahydrofuran, N,N-dimethylformamide,N,N-dimethylacetamide or acetonitrile, to generate a compound of formulaVIII, wherein R₄, R₅ and R₂ are as described under formula I above; stepii. nitration of compound VIII into compound IX, wherein R₄, R₅ and R₂are as described under formula I above, under classical conditionsdescribed for example in Advanced Organic Chemistry: Reactions,Mechanisms, and Structure, Fourth Edition by Jerry March, 1992(Publisher Wiley New York, N.Y.) p 523-525; and finally step iii.reduction of compound IX into compound III under classical conditionsdescribed for example in Advanced Organic Chemistry: Reactions,Mechanisms, and Structure, Fourth Edition by Jerry March, 1992(Publisher Wiley New York, N.Y.) p 1216-1217.

Alternatively, compounds of formula III, wherein R₂, R₄ and R₅ are asdescribed under formula I above, can also be prepared from compounds offormula XI, wherein R₂, R₄ and R₅ are as described under formula I, andin which X₁ is halogen, preferably chlorine or bromine (scheme 4).Compounds of formula XX, wherein R₂, R₄ and R₅ are as described underformula I above, and in which X₁ is halogen, preferably chlorine orbromine, and wherein PG is a protective group, such asC₁-C₆alkyl-carbonyl (for example acetyl) or haloC₁-C₆alkyl-carbonyl (forexample trifluoroacetyl), preferably PG is trifluoroacetyl, can beprepared by reacting compounds of formula XI, wherein R₂, R₄ and R₅ areas described under formula I, and in which X₁ is halogen, preferablychlorine or bromine, with an anhydride reagent of formula (R_(PG))₂O,wherein R_(PG) is C₁-C₆alkyl-carbonyl (for example (R_(PG))₂O is aceticanhydride) or haloC₁-C₆alkyl-carbonyl (for example (R_(PG))₂O istrifluoroacetic anhydride), preferably (R_(PG))₂O is trifluoroaceticanhydride (CF₃CO)₂O, optionally in presence of a base such astriethylamine, diisopropylethylamine or pyridine, optionally in presenceof an acylation catalyst such as 4-dimethylaminopyridine, in solventssuch as dichloromethane, tetrahydrofuran or dioxane, at temperaturesbetween 0 and 100° C., preferably between 0° C. and 30° C. Suchintroduction of specific protecting groups is very known to thoseskilled in the art, see for example Protective Groups in OrganicSynthesis, 3nd Ed Greene TW, Wuts PGM, 1999, pp 518-525.

Compounds of formula XXI, wherein R₂, R₄ and R₅ are as described underformula I above, and wherein PG is a protective group, such asC₁-C₆alkyl-carbonyl (for example acetyl) or haloC₁-C₆alkyl-carbonyl (forexample trifluoroacetyl), preferably PG is trifluoroacetyl, can beprepared by reacting compounds of formula XX, wherein R₂, R₄ and R₅ areas described under formula I above, and in which X₁ is halogen,preferably chlorine or bromine, and wherein PG is a protective group,such as C₁-C₆alkyl-carbonyl (for example acetyl) orhaloC₁-C₆alkyl-carbonyl (for example trifluoroacetyl), preferably PG istrifluoroacetyl, with for example sodium azide NaN₃, optionally inpresence of a complexant (such as, for example, 15-crown-5) that couldcomplex various cations, in an inert solvent such as tetrahydrofuran,dioxane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone or dimethyl sulfoxide (or mixtures thereof), attemperatures between 0 and 180° C., preferably between 20 and 150° C.,optionally under microwave irradiation.

Compounds of formula XXII, wherein R₂, R₄ and R₅ are as described underformula I above, can be prepared by reacting compounds of formula XXI,wherein R₂, R₄ and R₅ are as described under formula I above, andwherein PG is a protective group, such as C₁-C₆alkyl-carbonyl (forexample acetyl) or haloC₁-C₆alkyl-carbonyl (for exampletrifluoroacetyl), preferably PG is trifluoroacetyl, with a base such asalkali metal carbonates, for example lithium, sodium, potassium orcesium carbonate, in an alcohol solvent such as methanol, ethanol orisopropanol, optionally in presence of water, at temperatures between 0and 100° C., preferably between 0° C. and 30° C.

Compounds of formula III, wherein R₂, R₄ and R₅ are as described underformula I above, can be prepared by reacting compounds of formula XXII,wherein R₂, R₄ and R₅ are as described under formula I above, withtrivalent phosphorous compounds, for example trialkyl- ortriarylphosphines, preferably triphenylphosphine, and hydrolyzing insitu the generated iminophosphorane (or aza-ylide, Staudinger reaction)with water, optionally in presence of acid, such as hydrochloric orhydrobromic acid. Overall, azide compounds of formula XXII undergo aformal reduction to form primary amine compounds of formula III in thistransformation. This reaction may be performed in an inert solvent suchas tetrahydrofuran or dioxane, at temperatures between 0 and 180° C.,preferably between 20 and 150° C., optionally under microwaveirradiation. Alternatively, azido compounds of formula XXII may bereduced to amino compounds of formula III using molecular hydrogen (H₂),optionally under pressure, usually in the presence of a catalyst such asnickel, palladium or platinum, in inert solvents (such as for exampleethyl acetate, methanol or ethanol), at temperatures between 0° C. and120° C., preferably between 30° C. and reflux temperature.

Compounds of formula VII, wherein R₂ and R₄ are as described underformula I above, may be prepared by methods known to a person skilled inthe art. For example via: step 1.) the reaction of compound VIIa,wherein R₂ is as described under formula I above, with an appropriatehydroxylamine H₂NOR₄, or a salt thereof (such as a hydrohalide salt,preferably a hydrochloride or a hydrobromide salt, or any otherequivalent salt), wherein R₄ is as described under formula I above(scheme 5); followed by step 2.) cleavage of the benzoyl group byhydrolysis either under acidic (for example aqueous hydrochloric acid)or basic (for example lithium or sodium hydroxide, in an inert solventsuch as tetrahydrofuran or dioxane, optionally in presence of water)conditions. Compounds of formula VIIa, wherein R₂ is as described underformula I above, may prepared by methods known to a person skilled inthe art. See, for example, Synthesis 2005, No. 8, pp 1269-1278 andSynthesis 2011, No. 7, pp 1149-1156.

The preparation of compounds of formula XI, wherein R₂, R₄ and R₅ are asdescribed under formula I, and in which X₁ is halogen, preferablychlorine or bromine, is detailed below (see scheme 8).

Compounds of formula I-2, wherein Z is X—R₁ or a leaving group, forexample a halogen (preferably fluoro or chloro), and wherein X, R₁, R₂,R₃, R₄, R₅, R₆ and A are as described under formula I above, may beprepared by reaction between compounds of formula II respectively IIa,wherein Z is X—R₁ or a leaving group, for example a halogen (preferablyfluoro or chloro), and wherein X, R₁, R₃, R₆ and A are as describedunder formula I above, and in which X₀₀ is as described above, andcompounds of formula III, or a salt thereof, wherein R₄, R₅ and R₂ areas described under formula I above, under similar conditions as for thepreparation of compounds of formula Ia from compounds of formula II/IIaand III described above (see schemes 1 and 2). This is illustrated inscheme 6.

Compounds of formula I can be made by reacting compounds of compounds offormula I-2, wherein Z is a leaving group, for example a halogen(preferably fluoro or chloro) with compounds of formula V or Va asdescribed in scheme 3. All substituents are as defined above.

Alternatively, compounds of formula I-2, wherein Z is X—R₁ or a leavinggroup, for example a halogen (preferably fluoro or chloro), and whereinX, R₁, R₂, R₃, R₄, R₅, R₆ and A are as described under formula I above,can be prepared (scheme 7) by

i.) reaction between compounds of formula XI, or a salt thereof, whereinR₂, R₄ and R₅ are as described under formula I above, and in which X₁ isa leaving group, such as a halogen, preferably chlorine or bromine, andcompounds of formula II or IIa, wherein Z is X—R₁ or a leaving group,for example a halogen (preferably fluoro or chloro), and wherein X, R₁,R₃, R₆ and A are as described under formula I above, and in which X₀₀ isas described above, under similar conditions as for the preparation ofcompounds of formula VIa from compounds of formula II/IIa and IIIdescribed above (see scheme 2). This transformation generates compoundsof the formula X-2, wherein Z is X—R₁ or a leaving group, for example ahalogen (preferably fluoro or chloro), and wherein X, R₁, R₂, R₃, R₄,R₅, R₆ and A are as described under formula I above, and in which X₁ isa leaving group, such as a halogen, preferably chlorine or bromine;followed by

ii.) substitution of X₁, a leaving group, such as a halogen, preferablychlorine or bromine, in compounds of formula X-2 by an azido group toform compounds of formula X-3, wherein Z is X—R₁ or a leaving group, forexample a halogen (preferably fluoro or chloro), and wherein X, R₁, R₂,R₃, R₄, R₅, R₆ and A are as described under formula I above. Thistransformation is usually carried out in the presence of an azide saltsuch as, for example sodium azide NaN₃, optionally in presence of acomplexant (such as, for example, 15-crown-5) that could complex variouscations, in an inert solvent such as tetrahydrofuran, dioxane,acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone or dimethyl sulfoxide (or mixtures thereof), attemperatures between 0 and 180° C., preferably between 20 and 150° C.,optionally under microwave irradiation; further followed by iii.)formation of compounds of formula I-2, wherein Z is X—R₁ or a leavinggroup, for example a halogen (preferably fluoro or chloro), and whereinX, R₁, R₂, R₃, R₄, R₅, R₆ and A are as described under formula I above,from compounds of formula X-3 via a tandem Staudinger/cyclisationreaction. In this transformation, compounds of formula X-3, wherein Z isX—R₁ or a leaving group, for example a halogen (preferably fluoro orchloro), and wherein X, R₁, R₂, R₃, R₄, R₅, R₆ and A are as describedunder formula I above, are treated with trivalent phosphorous compounds,for example trialkyl- or triarylphosphines, preferablytriphenylphosphine, to in situ generate an iminophosphorane (oraza-ylide, Staudinger reaction) intermediate, which cyclises with theamide radical —NR₅C(O)— to form compounds of formula I-2. This reactionmay be performed in an inert solvent such as tetrahydrofuran, dioxane,toluene or xylene, at temperatures between 0 and 200° C., preferablybetween 20 and 180° C., optionally under microwave irradiation. TheStaudinger reaction is known to those skilled in the art, reaction ofits corresponding iminophosphorane (aza-ylide) with groups such ascarboxylic acid derivatives or ketones described in, for example,Strategic Applications of Named Reactions in Organic Synthesis by Kurti,Laszlo; Czako, Barbara; Editors; 2005, pp. 428-429. Alternatives arepossible, such as conditions described in, for example, Chemistry &Industry (London, United Kingdom) 1984, pp. 222-3.

Compounds of formula XI, wherein R₂, R₄ and R₅ are as described underformula I above, and in which X₁ is halogen, preferably chlorine orbromine, can be prepared (scheme 8) by i.) reacting compounds of formulacompound VIIa, wherein R₂ is as described under formula I above, with anappropriate hydroxylamine H₂NOR₄ (such as O-methyl hydroxylamine), or asalt thereof (such as a hydrohalide salt, preferably a hydrochloride ora hydrobromide salt, or any other equivalent salt), wherein R₄ is asdescribed under formula I above, under acidic conditions, for example inacetic (AcOH) or trifluoroacetic acid, optionally in presence of afurther inert solvent or diluent, such as dichloromethane, toluene,tetrahydrofuran THF or dioxane to form compounds of formula XVII,wherein R₂ and R₄ are as described under formula I above. The reactiontemperature can preferentially range from room temperature to theboiling point of the reaction mixture, or alternatively heating may beperformed under microwave irradiation; followed by either

iia.) reaction of compounds of formula XVII, wherein R₂ and R₄ are asdescribed under formula I above, under acidic conditions, for example inhydrochloric or acetic acid, to form compounds of formula XVI, whereinR₂ and R₄ are as described under formula I above, by dehydration. Thereaction temperature can preferentially range from room temperature tothe boiling point of the reaction mixture, or alternatively heating maybe performed under microwave irradiation. Further, reacting compounds offormula XVI, with, for example, di-tert-butyl dicarbonate (BOCanhydride, BOC₂O), in presence of a base, such as triethylamine NEt₃,diisopropylethylamine or pyridine, optionally in presence of anacylation catalyst such as 4-dimethylaminopyridine DMAP, in an inertsolvent such as dichloromethane DCM, tetrahydrofuran, dioxane ortoluene, at temperatures between 0 and 100° C., preferably between 0° C.and 30° C., to form compounds of formula XV, wherein R₂ and R₄ are asdescribed under formula I above, and in which PG is, for example, theBOC group —C(O)Ot-Bu (t-butyloxycarbonyl). Such introduction of specificprotecting groups is very known to those skilled in the art, see forexample Protective Groups in Organic Synthesis, 3nd Ed Greene TW, WutsPGM, 1999, pp 518-525; or alternatively

iib.) reaction of compounds of formula XVII, wherein R₂ and R₄ are asdescribed under formula I above, with, for example, di-tert-butyldicarbonate (BOC anhydride, BOC₂O), preferably at least two equivalents,in presence of a base, such as triethylamine NEt₃, diisopropylethylamineor pyridine, preferably at least two equivalents, optionally in presenceof an acylation catalyst such as 4-dimethylaminopyridine DMAP, in aninert solvent such as dichloromethane DCM, tetrahydrofuran, dioxane ortoluene, at temperatures between 0 and 100° C., preferably between 0° C.and 30° C., to directly form compounds of formula XV, wherein R₂ and R₄are as described under formula I above, and in which PG is, for example,the BOC group —C(O)Ot-Bu (t-butyloxycarbonyl) via tandem formaldehydration/BOC group introduction; followed byiii.) cleavage of the benzoyl group in compounds of formula XV byhydrolysis either under acidic (for example aqueous hydrochloric acid)or basic (for example lithium or sodium hydroxide, in an inert solventsuch as tetrahydrofuran or dioxane, optionally in presence of water)conditions, at temperatures between 0 and 100° C., preferably between 0°C. and 50° C., to form compounds of formula XIV, wherein R₂ and R₄ areas described under formula I above, and in which PG is, for example, theBOC group —C(O)Ot-Bu (t-butyloxycarbonyl); followed byiv.) alkylation of compounds of formula XIV, wherein R₂ and R₄ are asdescribed under formula I above, and in which PG is, for example, theBOC group —C(O)Ot-Bu (t-butyloxycarbonyl), with a reagent R₅—X_(LG),wherein R₅ is as described under formula I above and wherein X_(LG) is aleaving group, such as halogen, preferably iodine, bromine or chlorine(for example is R₅—X_(LG) is methyl iodide MeI), in presence of a base,such as sodium carbonate, potassium carbonate or cesium carbonate, orsodium hydride NaH, in a appropriate solvent such as for exampletetrahydrofuran THF, N,N-dimethylformamide, N,N-dimethylacetamide oracetonitrile, at temperatures between −20 and 100° C., preferablybetween 0° C. and 80° C., to form compounds of formula XIII, wherein R₄,R₅ and R₂ are as described under formula I above, and in which PG is,for example, the BOC group —C(O)Ot-Bu (t-butyloxycarbonyl); followed byv.) cleavage of the protective group PG, for example the BOC group—C(O)Ot-Bu (t-butyloxycarbonyl), in compounds of formula XIII, usuallyby hydrolysis either under acidic (for example aqueous hydrochloricacid) or basic (for example lithium or sodium hydroxide, in an inertsolvent such as tetrahydrofuran or dioxane, optionally in presence ofwater) conditions, or by acidic treatment (for example withtrifluoroacetic acid, or acetic acid in hydrobromic acid, or a solutionof hydrochloric or hydrobromic acid in an inert solvent, such astetrahydrofuran, dioxane or methanol), at temperatures between 0 and100° C., preferably between 0 and 80° C., to form compounds of formulaXII, wherein R₂, R₄ and R₅ are as described under formula I above. Suchconditions are known to a person skilled in the art. When the protectivegroup is preferably BOC, then the cleavage conditions are preferably,optionally aqueous, hydrogen chloride, or trifluoroacetic acid,optionally in the presence of a solvent, such as 1,4-dioxane,tetrahydrofuran or dichloromethane, at reaction temperatures rangingpreferentially from 0° C. to the boiling point of the reaction mixture,or the reaction may be performed under microwave irradiation; followedbyvi.) reaction of compounds of formula XII, wherein R₂, R₄ and R₅ are asdescribed under formula I above, with a halogenating agent such asN-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS), or alternativelychlorine or bromine. Such halogenation reactions are carried out in aninert solvent, such as chloroform, carbon tetrachloride,1,2-dichloroethane, acetic acid, ethers, acetonitrile orN,N-dimethylformamide DMF, at temperatures between 20-200° C.,preferably room temperature to 100° C., to form compounds of formula XI,wherein R₂, R₄ and R₅ are as described under formula I above, and inwhich X₁ is halogen, preferably chlorine or bromine. Such reactions arewell known to those skilled in the art, and have been described in, forexample, Advanced Organic Chemistry: Reactions, Mechanisms, andStructure, Fourth Edition by Jerry March, 1992 (Publisher Wiley NewYork, N.Y.) p 704-707.

The subgroup of compounds of the formula I-2, wherein Z is X—R₁, andwherein X, R₁, R₂, R₄, R₅, R₆ and A are as described under formula Iabove, and in which R₃ is a leaving group LG, for example a halogen or asulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate, may be represented by the formula I-2a(scheme 9).

Compounds of formula I, wherein X is SO or SO₂, and in which R₁, R₂, R₃,R₄, R₅, R₆ and A are as described under formula I above, can also beprepared by by a Suzuki reaction (scheme 9), which involves for example,reacting compounds of formula I-2a, wherein X is SO or SO₂, and in whichR₁, R₂, R₄, R₅, R₆ and A are as described under formula I above, and inwhich LG is a leaving group, for example a halogen or a sulfonate,preferably chlorine, bromine, iodine or trifluoromethanesulfonate, withcompounds of formula XVIII, wherein R₃ is as defined above, and whereinY_(b1) can be a boron-derived functional group, such as for exampleB(OH)₂ or B(OR_(b1))₂ wherein R_(b1) can be a C₁-C₄alkyl group or thetwo groups OR_(b1) can form together with the boron atom a five orsix-membered ring, as for example a pinacol boronic ester. The reactionmay be catalyzed by a palladium based catalyst, for exampletetrakis(triphenylphosphine)-palladium(0),(1,1′bis(diphenylphosphino)ferrocene)dichloro-palladium-dichloromethane(1:1 complex) orchloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(III)(XPhos palladacycle), in presence of a base, like sodium carbonate,tripotassium phosphate or cesium fluoride, in a solvent or a solventmixture, like, for example dioxane, acetonitrile, N,N-dimethylformamide,a mixture of 1,2-dimethoxyethane and water or of dioxane/water, or oftoluene/water, preferably under inert atmosphere. The reactiontemperature can preferentially range from room temperature to theboiling point of the reaction mixture, or the reaction may be performedunder microwave irradiation. Such Suzuki reactions are well known tothose skilled in the art and have been reviewed, for example, in J.Orgmet. Chem. 576, 1999, 147-168.

Alternatively, compounds of formula I, wherein X is SO or SO₂, may beprepared by a Stille reaction between compounds of formula XVIIIa,wherein R₃ is as defined above, and wherein Y_(b2) is a trialkyl tinderivative, preferably tri-n-butyl tin or tri-methyl tin, and compoundsof formula I-2a, wherein X is SO or SO₂, and in which R₁, R₂, R₄, R₅, R₆and A are as described under formula I above, and in which LG is aleaving group, for example a halogen or a sulfonate, preferablychlorine, bromine, iodine or trifluoromethanesulfonate. Such Stillereactions are usually carried out in the presence of a palladiumcatalyst, for example tetrakis(triphenylphosphine)palladium(0), orbis(triphenylphosphine) palladium(II) dichloride, in an inert solventsuch as N,N-dimethylformamide, acetonitrile, toluene or dioxane,optionally in the presence of an additive, such as cesium fluoride, orlithium chloride, and optionally in the presence of a further catalyst,for example copper(I)iodide. Such Stille couplings are also well knownto those skilled in the art, and have been described in for example J.Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74, 5599-5602, andAngew. Chem. Int. Ed., 2004, 43, 1132-1136.

When R₃ is a five-membered aromatic ring system linked via a nitrogenatom to the ring which contains the group A, then compounds of formulaI, wherein X is SO or SO₂, may be prepared from compounds of formulaI-2a, wherein X is SO or SO₂, and in which R₁, R₂, R₄, R₅, R₆ and A areas described under formula I above, and in which LG is a leaving group,for example a halogen or a sulfonate, preferably chlorine, bromine,iodine or trifluoromethanesulfonate, by reaction with a heterocycle R₃—H(which contains an appropriate NH functionality) XVIIIaa (for exampleXVIIIaa is 1H-1,2,4-triazole), wherein R₃ is as defined above, in thepresence of a base, such as potassium carbonate K₂CO₃ or cesiumcarbonate Cs₂CO₃, optionally in the presence of a copper catalyst, forexample copper(I) iodide, with or without an additive such as L-proline,N,N′-dimethylcyclohexane-1,2-diamine or N,N′-dimethylethylenediamine, inan inert solvent such as N-methylpyrrolidone NMP orN,N-dimethylformamide DMF at temperatures between 30-150° C., optionallyunder microwave irradiation.

Oxidation of compounds of formula I-2a, wherein X is (sulfide), and inwhich R₁, R₂, R₄, R₅, R₆ and A are as described under formula I above,and in which LG is a leaving group, for example a halogen or asulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate, with a suitable oxidizing agent, intocompounds of formula I-2a, wherein X is SO or SO₂, may be achieved underconditions already described above.

A large number of compounds of the formula XVIII, XVllla and XVIIIaa arecommercially available or can be prepared by those skilled in the art.

Alternatively, compounds of formula I, wherein X is SO or SO₂, may beprepared from compounds of formula I-2a, wherein X is S (sulfide) byinvolving the same chemistry as described above, but by changing theorder of the steps (i.e. by running the sequence I-2a (X is S) to I (Xis S) via Suzuki, Stille or C—N bond formation, followed by an oxidationstep to form I (X is SO or SO₂).

The subgroup of compounds of the formula I-2, wherein Z is X—R₁, andwherein X, R₁, R₂, R₄, R₅, R₃ and A are as described under formula Iabove, and in which R₆ is a leaving group LG, for example a halogen or asulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate, may be represented by the formula I-2b(scheme 10).

The chemistry described previously in scheme 9 can be appliedanalogously for the preparation of compounds of formula I, wherein X isS, SO or SO₂, and in which R₁, R₂, R₃, R₄, R₅, R₆ and A are as describedunder formula I above, by starting from compounds of the formula I-2b,wherein X is S, SO or SO₂, and in which R₁, R₂, R₄, R₅, R₃ and A are asdescribed under formula I above, and in which LG is a leaving group, forexample a halogen or a sulfonate, preferably chlorine, bromine, iodineor trifluoromethanesulfonate (scheme 10). Substituent definitionsmentioned previously in scheme 9 are also valid for thecompounds/reagents shown in scheme 10.

Compounds of formula I-2a and I-2b, wherein the substituents are asdefined above, may be prepared (scheme 10a) by reaction betweencompounds of formula II, respectively IIa, wherein the substituents areas defined above with the particular situation that either R₃ or R₆ arereplaced with LG, which is as defined above, and in which X₀₀ is asdescribed above (X₀₀ typically is chlorine), and compounds of formulaIII, or a salt thereof, wherein R₄, R₅ and R₂ are as described underformula I above, under similar conditions as for the preparation ofcompounds of formula Ia from compounds of formula II/IIa and IIIdescribed above (see schemes 1 and 2; see also scheme 6).

This is exemplified in scheme 10a for the synthesis of compounds offormula I-2b, wherein X, R₁, R₂, R₄, R₅, R₃ and A are as described underformula I above, and in which LG is a leaving group, for example ahalogen or a sulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate, that may be prepared by reaction betweencompounds of formula II-10, respectively their activated form II-10a,wherein X, R₁, R₃ and A are as described under formula I above, and inwhich LG is a leaving group, for example a halogen or a sulfonate,preferably chlorine, bromine, iodine or trifluoromethanesulfonate, andin which X₀₀ is as described above (X₀₀ typically is chlorine), andcompounds of formula III, or a salt thereof, wherein R₄, R₅ and R₂ areas described under formula I above, via compounds of formula X-10 andX-10a.

The subgroup of compounds of the formula I-2b, wherein A is N, andwherein X, R₁, R₂, R₄, R₅ and R₃ are as described under formula I above,and in which R₆ is a leaving group LG, for example a halogen, preferablychlorine or bromine, may be represented by the formula I-2b′ (scheme10b). Compounds of the formula I-2b′ can also be prepared asillustrated:

Compounds of the formula I, wherein A is N, and in which R₆ is hydrogen,and wherein X, R₁, R₂, R₃, R₄ and R₅ are as described under formula Iabove (represented by the formula Ic), can be oxidized to theircorresponding N-oxides Id under standard conditions already detailedabove (for example, m-chloroperoxybenzoic acid (mCPBA) indichloromethane at temperatures between room temperature and refluxingconditions), or alternatively by using a suitable oxidizing agent, forexample the H₂O₂/urea adduct in the presence of an acid anhydride, e.g.trifluoroacetic anhydride. Such oxidations are known from theliterature, for example from J. Med. Chem. 1989, 32, 2561 or WO00/15615. Compounds of the formula I-2b′, wherein X, R₁, R₂, R₄, R₅ andR₃ are as described under formula I above, and in which LG is a leavinggroup, for example a halogen, preferably chlorine or bromine, can beprepared by reacting N-oxide compounds of the formula Id, wherein X, R₁,R₂, R₃, R₄ and R₅ are as described under formula I above, with reagentssuch as, for example, phosphorus oxychloride or phosphorus trichloride,under conditions known to a person skilled in the art, and described in,for example, Scriven, E. F. V. (1984). “Pyridines and their BenzoDerivatives: (ii) Reactivity at Ring Atoms”. In Katritzky, Alan R.;Rees, Charles Wayne; Meth-Cohn, Otto. Comprehensive HeterocyclicChemistry: The Structure, Reactions, Synthesis and Uses of HeterocyclicCompounds. 2. Pergamon Press. pp. 165-314.

The subgroup of compounds of the formula I, wherein X, R₁, R₂, R₄, R₅,R₆ and A are as described under formula I above, and in which R₃ isC₃-C₆cycloalkyl which can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, cyano and C₁-C₄alkoxy, may be prepared by methodsdescribed above (in particular, compounds of formula I wherein R₃ iscyclopropyl may be prepared from compounds of formula I-2a, wherein LGis for example bromine, by a Suzuki reaction involvingcyclopropylboronic acid according to descriptions made in scheme 9). Forthe special case of compounds of formula I wherein R₃ is C₃-C₆cycloalkylsubstituted by cyano (represented by compounds of formula I-2e), thecompounds can be prepared by the methods shown in scheme 11.

Treatment of compounds of formula I-2a, wherein X, R₁, R₂, R₄, R₅, R₆and A are as described under formula I above, and in which LG is aleaving group, for example a halogen or a sulfonate, preferablychlorine, bromine, iodine or trifluoromethanesulfonate, withtrimethylsilyl-acetonitrile TMSCN, in the presence of zinc(II)fluorideZnF₂, and a palladium(0)catalyst such astris(dibenzylideneacetone)di-palladium(0)-chloroform adduct (Pd₂(dba)₃),with a ligand, for example Xantphos, in an inert solvent, such asN,N-dimethylformamide DMF at temperatures between 100-180° C.,optionally under microwave heating, may lead to compounds of formulaI-2e1, wherein X, R₁, R₂, R₄, R₅, R₆ and A are as described underformula I above. Such chemistry has been described in the literature,e.g. in Org. Lett. 16(24), 6314-6317, 2014. Alternatively, reaction ofcompounds of formula I-2a, wherein X, R₁, R₂, R₄, R₅, R₆ and A are asdescribed under formula I above, and in which LG is a leaving group, forexample a halogen or a sulfonate, preferably chlorine, bromine, iodineor trifluoromethanesulfonate, with 4-isoxazoleboronic acid or4-isoxazoleboronic acid pinacol ester, in the presence of potassiumfluoride KF, and a palladium catalyst such asbis(triphenylphosphine)palladium(II) dichloride Pd(PPh₃)₂Cl₂, in aninert solvent, such as dimethylsulfoxide DMSO, optionally in mixturewith water, at temperatures between 40-150° C., optionally undermicrowave heating, may lead to compounds of formula I-2e2, wherein X,R₁, R₂, R₄, R₅, R₆ and A are as described under formula I above.Reaction of compounds of formula I-2e2, wherein X, R₁, R₂, R₄, R₅, R₆and A are as described under formula I above, with aqueous potassiumfluoride KF (concentration between 0.5 and 3M, preferably 1M), in aninert solvent, such as dimethylsulfoxide DMSO or methanol, attemperatures between 20-150° C., optionally under microwave heating, mayalso lead to compounds of formula I-2e1, wherein X, R₁, R₂, R₄, R₅, R₆and A are as described under formula I above. Such chemistry has beendescribed in the literature, e.g. in J Am Chem Soc 2011, 133, 6948-6951.

Compounds of formula I-2e1, wherein X, R₁, R₂, R₄, R₅, R₆ and A are asdescribed under formula I above, can be further treated with compoundsof formula XXXII, wherein Qx is a direct bond or is (CH₂)_(n) and n is1, 2 or 3, and in which Xb₁₀ is a leaving group such as a halogen(preferably chlorine, bromine or iodine), in the presence of a base suchas sodium hydride, sodium carbonate, potassium carbonate K₂CO₃, orcesium carbonate Cs₂CO₃, in an inert solvent such asN,N-dimethylformamide DMF, acetone, or acetonitrile, at temperaturesbetween 0-120° C., to give compounds of formula I-2e, wherein X, R₁, R₂,R₄, R₅, R₆ and A are as described under formula I above, and in which Qxis a direct bond or is (CH₂)_(n) and n is 1, 2 or 3. Alternatively,compounds of formula I-2e can be prepared directly from compounds offormula I-2a by treatment with compounds of formula XXXIII, wherein Qxis as described in XXXII, in presence of a catalyst such as Pd₂(dba)₃,with a ligand, such as BINAP, a strong base such as lithiumhexamethyldisilazane LiHMDS, in an inert solvent such as tetrahydrofuranTHF, at temperatures between 30-80° C. Such chemistry has been describedin, for example, J. Am. Chem. Soc. 127(45), 15824-15832, 2005.

Yet another method to prepare compounds of formula I-2e1 from compoundsof formula I-2a is shown below (scheme 12). Reaction of compounds offormula I-2a, wherein X, R₁, R₂, R₄, R₅, R₆ and A are as described underformula I above, and in which LG is a leaving group, for example ahalogen or a sulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate, with reagents of the formula XXXIV, whereinRx is C₁-C₆alkyl, in the presence of a base, such as sodium carbonate,potassium carbonate or cesium carbonate, or sodium hydride, sodiummethoxide or ethoxide, potassium tert-butoxide, optionally underpalladium (for example involving Pd(PPh₃)₂Cl₂) or copper (for exampleinvolving CuI) catalysis, in a appropriate solvent such as for exampletoluene, dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide,N,N-dimethylacetamide, N-methyl-2-pyrrolidone NMP or dimethylsulfoxideDMSO, optionally in presence of a phase transfer catalyst PTC, such asfor example tetrabutyl ammonium bromide or triethyl benzyl ammoniumchloride TEBAC, at temperatures between room temperature and 180° C.,may lead to compounds of formula I-2e3, wherein X, R₁, R₂, R₄, R₅, R₆and A are as described under formula I above, and in which Rx isC₁-C₆alkyl. Similar chemistry has been described in, for example,Synthesis 2010, No. 19, 3332-3338.

Compounds of formula I-2e1, wherein X, R₁, R₂, R₄, R₅, R₆ and A are asdescribed under formula I above, may be prepared bysaponification/decarboxylation of the compounds of formula I-2e3,wherein X, R₁, R₂, R₄, R₅, R₆ and A are as described under formula Iabove, and in which Rx is C₁-C₆alkyl, under conditions known to a personskilled in the art (using for example conditions such as: aqueoussodium, potassium or lithium hydroxide in methanol, ethanol,tetrahydrofuran or dioxane at room temperature, or up to refluxingconditions; followed by acificationi of the reaction mixture understandard aqueous acid conditions). Alternatively, treating compounds offormula I-2e3 with halide anions, preferably chloride anions,originating from, for example, lithium chloride or sodium chloride, insolvents such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone or dimethylsulfoxide DMSO, optionally in presenceof additional water, may also generate the compounds of formula I-2e1.The reaction temperature for such a transformation (KrapchoO-dealkyla-tion/decarboxylation) range preferentially from 20° C. to theboiling point of the reaction mixture, or the reaction may be performedunder microwave irradiation. Similar chemistry has been described in,for example, Synthesis 2010, No. 19, 3332-3338.

Alternatively compounds of formula I-2e, wherein X, R₁, R₂, R₄, R₅, R₆and A are as described under formula I above, and in which Qx is adirect bond or is (CH₂)_(n) and n is 1, 2 or 3, can also be prepared asshown in schemes 13 and 14.

Compounds of formula II-4, wherein X, R₁, R₆ and A are as describedunder formula I above, and in which Qx is a direct bond or is (CH₂)_(n)and n is 1, 2 or 3, and wherein Rx₁ is C₁-C₆alkyl, can be prepared(scheme 13) from compounds of formula II-1, wherein X, R₁, R₆ and A areas described under formula I above, and in which LG is a leaving group,for example a halogen or a sulfonate, preferably chlorine, bromine,iodine or trifluoromethanesulfonate, and wherein Rx₁ is C₁-C₆alkyl, inanalogy to chemistry described and discussed in schemes 11 and 12, viaintermediates II-2, II-3, II-5, or directly, and involving said reactionconditions and reagents of formula XXXII or XXXIII.

Compounds of formula II-6, wherein X, R₁, R₆ and A are as describedunder formula I above, and in which Qx is a direct bond or is (CH₂)_(n)and n is 1, 2 or 3, can be prepared (scheme 14) by saponification of thecompounds of formula II-4, wherein X, R₁, R₆ and A are as describedunder formula I above, and in which Qx is a direct bond or is (CH₂)_(n)and n is 1, 2 or 3, and wherein Rx₁ is C₁-C₆alkyl, under conditionsknown to a person skilled in the art (using for example conditions suchas: sodium, potassium or lithium hydroxide in methanol, ethanol,tetrahydrofuran or dioxane, optionally in presence of water, at roomtemperature, or up to refluxing conditions).

Compounds of formula I-2e, wherein X, R₁, R₂, R₄, R₅, R₆ and A are asdescribed under formula I above, and in which Qx is a direct bond or is(CH₂)_(n) and n is 1, 2 or 3, can be prepared (scheme 14) by reactionbetween compounds of formula II-6, respectively their activated formII-6a, wherein X, R₁, R₆ and A are as described under formula I above,and in which Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or 3, andin which X₀₀ is as described above (X₀₀ typically is chlorine), andcompounds of formula III, or a salt thereof, wherein R₄, R₅ and R₂ areas described under formula I above, under similar conditions as for thepreparation of compounds of formula Ia from compounds of formula II/IIaand III described above (see schemes 1 and 2; see also scheme 6), andvia compounds of formula X-4 and X-4a.

The subgroup of compounds of the formula I, wherein X, R₁, R₂, R₄, R₅,R₆ and A are as described under formula I above, and in which R₃ isC₁-C₄alkyl, may be prepared by methods described above (for example,compounds of formula I wherein R₃ is isopropyl may be prepared fromcompounds of formula I-2a, wherein LG is for example bromine, by aSuzuki reaction involving isopropylboronic acid pinacol ester accordingto descriptions made in scheme 9). For the special case of compounds offormula I wherein R₃ is C₁-C₄alkyl monosubstituted by cyano, preferablyisopropyl monosubstituted by cyano (represented by compounds of formulaI-2f), the compounds can be prepared by the methods shown in scheme 15.

Compounds of formula I-2f, wherein X, R₁, R₂, R₄, R₅, R₆ and A are asdescribed under formula I above, may be prepared by reacting compoundsof formula I-2e1, wherein X, R₁, R₂, R₄, R₅, R₆ and A are as describedunder formula I above, with reagents of formula XXXV, wherein Xb₁₀ is aleaving group such as a halogen (preferably chlorine, bromine oriodine), alternatively with dimethylsulfate, in the presence of a basesuch as sodium hydride, sodium carbonate, potassium carbonate K₂CO₃, orcesium carbonate Cs₂CO₃, in an inert solvent such asN,N-dimethylformamide DMF, acetone, or acetonitrile, at temperaturesbetween 0-120° C. Alternatively, compounds of formula I-2f may beprepared directly from compounds of formula I-2a by treatment withcompounds of formula XXXVI, optionally in presence of a catalyst such asPd₂(dba)₃, with a ligand, such as BINAP, and a strong base such aslithium hexamethyldisilazane LiHMDS, in an inert solvent such astetrahydrofuran THF, dioxane or 1,2-dimethoxyethane, at temperaturesbetween −30° C. to 80° C. Such chemistry has been described in, forexample, J. Am. Chem. Soc. 127(45), 15824-15832, 2005. Options toprepare compounds of formula I-2e1 from compounds I-2a, possibly viaintermediates of formula I-2e2 or I-2e3, have been detailed above inschemes 11 and 12.

Alternatively, compounds of formula I-2f, wherein X, R₁, R₂, R₄, R₅, R₆and A are as described under formula I above, can also be prepared asshown in schemes 16 and 17.

Compounds of formula II-7, wherein X, R₁, R₆ and A are as describedunder formula I above, and wherein Rx₁ is C₁-C₆alkyl, can be prepared(scheme 16) by reacting compounds of formula II-2, wherein X, R₁, R₆ andA are as described under formula I above, and in which Rx₁ isC₁-C₆alkyl, with reagents of formula XXXV, wherein Xb₁₀ is a leavinggroup such as a halogen (preferably chlorine, bromine or iodine),alternatively with dimethylsulfate, in the presence of a base such assodium hydride, sodium carbonate, potassium carbonate K₂CO₃, or cesiumcarbonate Cs₂CO₃, in an inert solvent such as N,N-dimethylformamide DMF,acetone, or acetonitrile, at temperatures between 0-120° C.Alternatively, compounds of formula II-7 may be prepared directly fromcompounds of formula II-1 by treatment with compounds of formula XXXVI,optionally in presence of a catalyst such as Pd₂(dba)₃, with a ligand,such as BINAP, and a strong base such as lithium hexamethyldisilazaneLiHMDS, in an inert solvent such as tetrahydrofuran THF, dioxane or1,2-dimethoxyethane, at temperatures between −30° C. to 80° C. Suchchemistry has been described in, for example, J. Am. Chem. Soc. 127(45),15824-15832, 2005. Options to prepare compounds of formula II-2 fromcompounds II-1, possibly via intermediates of formula II-3 or II-5, havebeen detailed above in scheme 13 (see also conditions described inschemes 11 and 12).

Compounds of formula II-8, wherein X, R₁, R₆ and A are as describedunder formula I above, can be prepared (scheme 17) by saponification ofthe compounds of formula II-7, wherein X, R₁, R₆ and A are as describedunder formula I above, and wherein Rx₁ is C₁-C₆alkyl, under conditionsknown to a person skilled in the art (using for example conditions suchas: sodium, potassium or lithium hydroxide in methanol, ethanol,tetrahydrofuran or dioxane, optionally in presence of water, at roomtemperature, or up to refluxing conditions).

Compounds of formula I-2f, wherein X, R₁, R₂, R₄, R₅, R₆ and A are asdescribed under formula I above, can be prepared (scheme 17) by reactionbetween compounds of formula II-8, respectively their activated formII-8a, wherein X, R₁, R₆ and A are as described under formula I above,and in which X₀₀ is as described above (X₀₀ typically is chlorine), andcompounds of formula III, or a salt thereof, wherein R₄, R₅ and R₂ areas described under formula I above, under similar conditions as for thepreparation of compounds of formula Ia from compounds of formula II/IIaand III described above (see schemes 1 and 2; see also schemes 6 and14), and via compounds of formula X-5 and X-5a.

Compounds of formula I, wherein R₆ is labeled as R_(6(amino)), definethe particular subgroup of compounds of formula I, wherein R₆ is NR₇R₈,and in which R₇ and R₈ are independently hydrogen, C₁-C₄alkyl orC₃-C₆cycloalkyl, preferably hydrogen, methyl, ethyl or cyclopropyl.Compounds of formula I-2g, or a salt thereof, wherein R₆ isR_(6(amino)), and wherein X, R₁, R₂, R₄, R₅, R₃ and A are as describedunder formula I above,

can be prepared (scheme 18) by an amination reaction, which involves forexample, reacting compounds of formula I-2b (see scheme 10), wherein X,R₁, R₂, R₄, R₅, R₃ and A are as described under formula I above, and inwhich LG is a leaving group, for example a halogen or a sulfonate,preferably chlorine, bromine, iodine or trifluoromethanesulfonate, withamino reagents of formula XXXVII (ammonia) or formula XXXVIIIa (e.g.methylamine as a representative of C₁-C₄(cyclo)alkylamines H₂NR₇ [R₈ ishydrogen)], or dimethylamine as a representative ofC₁-C₄di(cyclo)alkylamines HNR₇R₈), or corresponding salts thereof (suchas a hydrohalide salt, preferably a hydrochloride or a hydrobromidesalt, or any other equivalent salt). The source for the reagent XXXVIImay be ammonia NH₃ or an ammonia equivalent such as for example ammoniumhydroxide NH₄OH, ammonium chloride NH₄Cl, ammonium acetate NH₄OAc,ammonium carbonate (NH₄)₂CO₃, and other NH₃ surrogates. Thistransformation is preferably performed in suitable solvents (ordiluents) such as alcohols, amides, esters, ethers, nitriles and water,particularly preferred are methanol, ethanol, 2,2,2-trifluoroethanol,propanol, iso-propanol, N,N-dimethylformamide, N,N-dimethylacetamide,dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate,water or mixtures thereof, optionally in presence of a base, attemperatures between 0-150° C., preferably at temperatures ranging fromroom temperature to the boiling point of the reaction mixture,optionally under microwave irradiation and optionally in a pressurizedvessel.

Compounds of formula I-2h, wherein R₆ is R_(6(amino)) as defined above,and in which R₃ is halogen (preferably chlorine, bromine or iodine), andwherein X, R₁, R₂, R₄, R₅ and A are as described under formula I above,can be prepared (scheme 18) by a halogenation reaction, which involvesfor example, reacting compounds of formula I-2g, wherein R₆ isR_(6(amino)) as defined above, and in which R₃ is hydrogen, and whereinX, R₁, R₂, R₄, R₅ and A are as described under formula I above, withhalogenating reagents such as N-chlorosuccinimide (NCS),N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), or alternativelychlorine, bromine or iodine. Such halogenation reactions are carried outin an inert solvent, such as chloroform, carbon tetrachloride,1,2-dichloroethane, acetic acid, ethers, acetonitrile orN,N-dimethylformamide, at temperatures between 20-200° C., preferablyroom temperature to 100° C.

Hydroxylamine compounds of formula H₂NOR₄ (such as O-methylhydroxylamine), or a salt thereof (such as a hydrohalide salt,preferably a hydrochloride or a hydrobromide salt, or any otherequivalent salt), wherein R₄ is as described under formula I above, areeither known, commercially available or may be made by methods known toa person skilled in the art.

A large number of compounds of the formula XVIII, XVIIIa, XVIIIaa,XVIII′, XVIIIa′, XVIIIaa′, XXXII, XXXIII, XXXIV, XXXV, XXXVI andXXXVIIIa are either known, commercially available or may be made bymethods known to a person skilled in the art.

Compounds of formula II

wherein Z is X—R₁ or a leaving group, for example a halogen (preferablyfluoro or chloro), and wherein X, R₁, R₃, R₆ and A are as describedunder formula I above, as well as obvious close analogues such as esterderivatives of compounds II (e.g. a methyl or ethyl ester), representedby the formula lib, wherein Rx₁ is C₁-C₆alkyl, are either known,commercially available (for example3-ethylsulfanyl-pyridine-2-carboxylic acid) or may be made underconditions known to a person skilled in the art. In particular,C₁-C₆alkyl esters IIb of acid compounds of the formula II may beobtained by treating said acids II with the appropriate alcohols Rx₁-OH,in presence of a catalytic amount of acid (e.g. sulfuric acid), understandard conditions. Respectively, saponification under standardconditions (scheme 14) of esters of formula IIb will generate the acidof formula II.

Similar considerations apply to the compounds of formula II-1,respectively II-1′

wherein X, R₁, R₆ and A are as described under formula I above, and inwhich Rx₁ is C₁-C₆alkyl, and wherein LG is a leaving group, for examplea halogen or a sulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate. For example,5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid is known from WO2016/005263, or methyl 4-bromo-2-ethylsulfanyl-benzoate from WO2016/023954.

Similar considerations apply also to the compounds of formula II-10,respectively II-10′

wherein X, R₁, R₃ and A are as described under formula I above, and inwhich Rx₁ is C₁-C₆alkyl, and wherein LG is a leaving group, for examplea halogen or a sulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate. For example,6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid is known from WO2017/001314, or methyl 5-chloro-2-ethylsulfanyl-benzoate from Synthesis2011, (21), 3429-3434.

Compounds of the formula Z-1

wherein R₂, and R₄ are as defined under formula I above;X₁ is halogen or azido; Ry is hydrogen or Boc (di-tert-butyldicarbonate)and Rz is C₁-C₄alkyl; are novel and especially prepared for thepreparation of the compounds of formula I and therefore constitute afurther object of this invention. The preferred embodiments of thesubstituents R₂ and R₄ as described under formula I above are also validfor the compounds of formula Z-1.

For preparing all further compounds of the formula (I) functionalizedaccording to the definitions of formula II and Q, there are a largenumber of suitable known standard methods, for example alkylation,halogenation, acylation, amidation, oximation, oxidation and reduction,the choice of the preparation methods which are suitable depending onthe properties (reactivity) of the substituents in the intermediates.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se intoanother compound of formula I by replacing one or more substituents ofthe starting compound of formula I in the customary manner by (an)othersubstituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties, can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomer'sthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med. Chem.1989, 32, 2561 or WO 00/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds according to the following Table 1 below can be preparedaccording to the methods described above. The examples which follow areintended to illustrate the invention and show preferred compounds offormula I. “Ph” represents the phenyl group.

Table 1: This table discloses the 48 compounds of the formula I-2c:

TABLE 1 Comp. No. X R₁ R₃ R₆ A R₂ R₄ R₅ 1.001 S —CH₂CH₃ H H N CF₃ CH₃CH₃ 1.002 SO₂ —CH₂CH₃ H H N CF₃ CH₃ CH₃ 1.003 S —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.004 SO₂ —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.005 S —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.006 SO₂ —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.007 S —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.008 SO₂ —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.009 S —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.010 SO₂ —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.011 S —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.012 SO₂ —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.013 S —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.014 SO₂ —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.015 S —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.016 SO₂ —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.017 S —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.018 SO₂ —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.019 S —CH₂CH₃ H NH₂ N CF₃ CH₃ CH₃ 1.020 SO₂ —CH₂CH₃ HNH₂ N CF₃ CH₃ CH₃ 1.021 S —CH₂CH₃ NH₂ H N CF₃ CH₃ CH₃ 1.022 SO₂ —CH₂CH₃NH₂ H N CF₃ CH₃ CH₃ 1.023 S —CH₂CH₃ Cl NH₂ N CF₃ CH₃ CH₃ 1.024 SO₂—CH₂CH₃ Cl NH₂ N CF₃ CH₃ CH₃ 1.025 S —CH₂CH₃ NH₂ Cl N CF₃ CH₃ CH₃ 1.026SO₂ —CH₂CH₃ NH₂ Cl N CF₃ CH₃ CH₃ 1.027 S —CH₂CH₃ H

C CF₃ CH₃ CH₃ 1.028 SO₂ —CH₂CH₃ H

C CF₃ CH₃ CH₃ 1.029 S —CH₂CH₃

H C CF₃ CH₃ CH₃ 1.03  SO₂ —CH₂CH₃

H C CF₃ CH₃ CH₃ 1.031 S —CH₂CH₃ H H C CF₃ CH₃ CH₃ 1.032 SO₂ —CH₂CH₃ H HC CF₃ CH₃ CH₃ 1.033 SO —CH₂CH₃ H H N CF₃ CH₃ CH₃ 1.034 SO —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.035 SO —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.036 SO —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.037 SO —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.038 SO —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.039 SO —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.040 SO —CH₂CH₃ H

N CF₃ CH₃ CH₃ 1.041 SO —CH₂CH₃

H N CF₃ CH₃ CH₃ 1.042 SO —CH₂CH₃ H NH₂ N CF₃ CH₃ CH₃ 1.043 SO —CH₂CH₃NH₂ H N CF₃ CH₃ CH₃ 1.044 SO —CH₂CH₃ Cl NH₂ N CF₃ CH₃ CH₃ 1.045 SO—CH₂CH₃ NH₂ Cl N CF₃ CH₃ CH₃ 1.046 SO —CH₂CH₃ H

C CF₃ CH₃ CH₃ 1.047 SO —CH₂CH₃

H C CF₃ CH₃ CH₃ 1.048 SO —CH₂CH₃ H H C CF₃ CH₃ CH₃and the N-oxides of the compounds of Table 1.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;from the order Anoplura, for example,Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.; from the order Coleoptera, for example,Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.; from the order Diptera, forexample,Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;from the order Hemiptera, for example,Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoeliai thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens; Acyrthosium pisum, Adalgesspp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp,Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus,Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiellaspp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani,Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicorynebrassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp.,Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp,Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum,Dalbulus maidis, Dialeurodes spp, Diaphorina citri, Diuraphis noxia,Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae,Hyalopterus spp, Hyperomyzus pallidus, Idioscopus clypealis, Jacobiascalybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphiserysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfapruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.,Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piriMats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae,Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinusmaidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcusspp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelisseriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp.,Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera,Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp,Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae,Unaspis citri, Zygina flammigera, Zyginidia scutellaris;from the order Hymenoptera, for example,Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplo-campa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;from the order Isoptera, for example,Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminatefrom the order Lepidoptera, for example,Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Gra-pholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypi-ela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;from the order Mallophaga, for example,Damalinea spp. and Trichodectes spp.;from the order Orthoptera, for example,Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;from the order Psocoptera, for example,Liposcelis spp.;from the order Siphonaptera, for example,Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;from the order Thysanoptera, for example,Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by8-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab,are known. In the case of modified toxins, one or more amino acids ofthe naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810). Examples of such toxins or transgenic plantscapable of synthesising such toxins are disclosed, for example, inEP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1 Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Btll Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Crops may also be modified for enhanced resistance to fungal (forexample Fusarium, Anthracnose, or Phytophthora), bacterial (for examplePseudomonas) or viral (for example potato leafroll virus, tomato spottedwilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes,such as the soybean cyst nematode.

Crops that are tolerance to abiotic stress include those that haveenhanced tolerance to drought, high salt, high temperature, chill,frost, or light radiation, for example through expression of NF—YB orother proteins known in the art.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store ambients and the protection ofraw materials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents. A further object of the inventionis therefore a substrate selected from nonwoven and fabric materialcomprising a composition which contains a compound of formula I.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 03/034823, U.S. Pat. No. 5,631,072, WO 2005/64072, WO2006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

The present invention may be also used to control any insect pests thatmay be present in turfgrass, including for example beetles,caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites,mole crickets, scales, mealybugs ticks, spittlebugs, southern chinchbugs and white grubs. The present invention may be used to controlinsect pests at various stages of their life cycle, including eggs,larvae, nymphs and adults.

In particular, the present invention may be used to control insect peststhat feed on the roots of turfgrass including white grubs (such asCyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp.(e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green Junebeetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica),Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Blackturfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic gardenbeetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.),mole crickets (tawny, southern, and short-winged; Scapteriscus spp.,Gryllotalpa africana) and leatherjackets (European crane fly, Tipulaspp.).

The present invention may also be used to control insect pests ofturfgrass that are thatch dwelling, including armyworms (such as fallarmyworm Spodoptera frugiperda, and common armyworm Pseudaletiaunipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatusverstitus and S. parvulus), and sod webworms (such as Crambus spp. andthe tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests ofturfgrass that live above the ground and feed on the turfgrass leaves,including chinch bugs (such as southern chinch bugs, Blissus insularis),Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug(Antonina graminis), two-lined spittlebug (Propsapia bicincta),leafhoppers, cutworms (Noctuidae family), and greenbugs.

The present invention may also be used to control other pests ofturfgrass such as red imported fire ants (Solenopsis invicta) thatcreate ant mounds in turf.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp.,Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The compounds according to the invention can be used as pesticidalagents in unmodified form, but they are generally formulated intocompositions in various ways using formulation adjuvants, such ascarriers, solvents and surface-active substances. The formulations canbe in various physical forms, e.g. in the form of dusting powders, gels,wettable powders, water-dispersible granules, water-dispersible tablets,effervescent pellets, emulsifiable concentrates, microemulsifiableconcentrates, oil-in-water emulsions, oil-flowables, aqueousdispersions, oily dispersions, suspo-emulsions, capsule suspensions,emulsifiable granules, soluble liquids, water-soluble concentrates (withwater or a water-miscible organic solvent as carrier), impregnatedpolymer films or in other forms known e.g. from the Manual onDevelopment and Use of FAO and WHO Specifications for Pesticides, UnitedNations, First Edition, Second Revision (2010). Such formulations caneither be used directly or diluted prior to use. The dilutions can bemade, for example, with water, liquid fertilisers, micronutrients,biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof.

The active ingredients can also be contained in very fine microcapsules.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into the environment incontrolled amounts (e.g. slow-release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be in the form of a monolithic solid, in the formof fine particles in solid or liquid dispersion or in the form of asuitable solution. The encapsulating membranes can comprise, forexample, natural or synthetic rubbers, cellulose, styrene/butadienecopolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart. Alternatively, very fine microcapsules can be formed in which theactive ingredient is contained in the form of finely divided particlesin a solid matrix of base substance, but the microcapsules are notthemselves encapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid,propyl lactate, propylene carbonate, propylene glycol, propylene glycolmethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol methyl ether, diethylene glycol methyl ether, methanol, ethanol,isopropanol, and alcohols of higher molecular weight, such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol,propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone,calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks,wheat flour, soybean flour, pumice, wood flour, ground walnut shells,lignin and similar substances.

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono- and di-alkylphosphate esters; and also further substancesdescribed e.g. in McCutcheon's Detergents and Emulsifiers Annual, MCPublishing Corp., Ridgewood N.J. (1981).

Further adjuvants that can be used in pesticidal formulations includecrystallisation inhibitors, viscosity modifiers, suspending agents,dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, andliquid and solid fertilisers.

The compositions according to the invention can include an additivecomprising an oil of vegetable or animal origin, a mineral oil, alkylesters of such oils or mixtures of such oils and oil derivatives. Theamount of oil additive in the composition according to the invention isgenerally from 0.01 to 10%, based on the mixture to be applied. Forexample, the oil additive can be added to a spray tank in the desiredconcentration after a spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. Preferred oil additives comprise alkyl esters of C₈-C₂₂ fattyacids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, forexample the methyl esters of lauric acid, palmitic acid and oleic acid(methyl laurate, methyl palmitate and methyl oleate, respectively). Manyoil derivatives are known from the Compendium of Herbicide Adjuvants,10^(th) Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of compounds of the presentinvention and from 1 to 99.9% by weight of a formulation adjuvant whichpreferably includes from 0 to 25% by weight of a surface-activesubstance. Whereas commercial products may preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on thenature of the soil, the method of application, the crop plant, the pestto be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. As a general guideline compounds may be applied at a rateof from 1 to 2000 I/ha, especially from 10 to 1000 I/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90%

surface-active agent: 1 to 30%, preferably 5 to 20%

liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Wettable powders a) b) c) active ingredients 25%  50% 75% sodiumlignosulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodium —  6% 10%diisobutylnaphthalenesulfonate phenol polyethylene —  2% — glycol etherethylene (7-8 mol of oxide) highly dispersed silicic acid 5% 10% 10%Kaolin 62%  27% —

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording wettable powders thatcan be diluted with water to give suspensions of the desiredconcentration.

Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75%light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — 20%

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Emulsifiable concentrate active ingredients 10% octylphenol polyethyleneglycol ether (4-5 mol of ethylene  3% oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol ofethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredients  5%  6%  4% Talcum 95% — — Kaolin —94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the combination with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry dressings for seed.

Extruder granules Active ingredients 15% sodium lignosulfonate  2%carboxymethylcellulose  1% Kaolin 82%

The combination is mixed and ground with the adjuvants, and the mixtureis moistened with water. The mixture is extruded and then dried in astream of air.

Coated granules Active ingredients 8% polyethylene glycol (mol. wt. 200)3% Kaolin 89% 

The finely ground combination is uniformly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Non-dusty coated granules areobtained in this manner.

Suspension concentrate active ingredients 40% propylene glycol 10%nonylphenol polyethylene glycol ether (15 mol of ethylene oxide)  6%Sodium lignosulfonate 10% carboxymethylcellulose  1% silicone oil (inthe form of a 75% emulsion in water)  1% Water 32%

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable concentrate for seed treatment active ingredients 40% propylene glycol 5% copolymer butanol PO/EO 2% Tristyrenephenole with10-20 moles EO 2% 1,2-benzisothiazolin-3-one 0.5%   (in the form of a20% solution in water) monoazo-pigment calcium salt 5% Silicone oil (inthe form of a 75% emulsion in water) 0.2%   Water 45.3%  

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromaticsolvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed. The obtainedcapsule suspension is stabilized by adding 0.25 parts of a thickener and3 parts of a dispersing agent.

The capsule suspension formulation contains 28% of the activeingredients. The medium capsule diameter is 8-15 microns. The resultingformulation is applied to seeds as an aqueous suspension in an apparatussuitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspensionconcentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), awater dispersible granule (WG), an emulsifiable granule (EG), anemulsion, water in oil (EO), an emulsion, oil in water (EW), amicro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable(OF), an oil miscible liquid (OL), a soluble concentrate (SL), anultra-low volume suspension (SU), an ultra-low volume liquid (UL), atechnical concentrate (TK), a dispersible concentrate (DC), a wettablepowder (WP), a soluble granule (SG) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Preparatory Examples

“Mp” means melting point in ° C. Free radicals represent methyl groups.¹H and ¹⁹F NMR measurements were recorded on Brucker 400 MHz or 300 MHzspectrometers, chemical shifts are given in ppm relevant to a TMSstandard. Spectra measured in deuterated solvents as indicated. Eitherone of the LCMS methods below was used to characterize the compounds.The characteristic LCMS values obtained for each compound were theretention time (“Rt”, recorded in minutes) and the measured molecularion (M+H)⁺ and/or (M−H)⁻.

LCMS Methods:

Method A—Standard: (SQD-ZDQ-ZCQ)

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Method B—Standard Long: (SQD-ZDQ-ZCQ)

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min0% B, 100% A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

Method C—Unpolar: (SQD-ZDQ-ZCQ)

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: gradient: 0 min40% B, 60% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Method D

Spectra were recorded on a Mass Spectrometer from Agilent Technologies(6410 Triple Quadruple Mass Spectrometer) equipped with an electrospraysource (Polarity: Positive and Negative Polarity Switch, Capillary: 4.00kV, Fragmentor: 100.00 V, Gas Temperature: 350° C., Gas Flow: 11 L/min,Nebulizer Gas: 45 psi, Mass range: 110-1000 Da, DAD Wavelength range:210-400 nm). Column: KINETEX EVO C18, length 50 mm, diameter 4.6 mm,particle size 2.6 μm. Column oven temperature 40° C. Solvent gradient:A=Water with 0.1% formic acid: Acetonitrile (95:5 v/v). B=Acetonitrilewith 0.1% formic acid. Gradient=0 min 90% A, 10% B; 0.9-1.8 min 0% A,100% B, 2.2-2.5 min 90% A, 10% B. Flow rate 1.8 mL/min.

Method E

Spectra were recorded on a Mass Spectrometer from Waters (Acquity SDSMass Spectrometer) equipped with an electrospray source (Polarity:Positive and Negative Polarity Switch, Capillary: 3.00 kV, Cone Voltage:41.00 V, Source temperature: 150° C., Desolvation Gas Flow: 1000 L/Hr,Desolvation temperature: 500° C., Gas Flow @Cone: 50 L/hr, Mass range:110-800 Da, PDA wavelength range: 210-400 nm.Column: Acquity UPLC HSS T3C18, length 30 mm, diameter 2.1 mm, particle size 1.8 μm. Column oventemperature 40° C. Solvent gradient: A=Water with 0.1% formic acid:Acetonitrile (95:5 v/v). B=Acetonitrile with 0.05% formic acid.Gradient=0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3 min 0% A,100% B; 1.4-1.6 min 90% A, 10% B. Flow rate 0.8 mL/min.

a) Synthesis of Intermediates Example I1: Preparation of4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

Step I1-A: Synthesis ofN-[2-hydroxy-1-methoxy-6-oxo-2-(trifluoromethyl)-3H-pyridin-5-yl]benzamide

To a solution of N-[2-oxo-6-(trifluoromethyl)pyran-3-yl]benzamide (28mmol, 8.0 g) in tetrahydrofuran (80 mL) was added O-methylhydroxylamine(42 mmol, 2.0 g) and acetic acid (56 mmol, 3.4 g, 3.2 mL). The reactionwas refluxed for 4-5 hours. After the reaction was completed, themixture was diluted with water (50 ml) and ethyl acetate (100 ml). Theorganic and aqueous phases were separated and the aqueous layer wasextracted with ethyl acetate (3×50 ml). Combined organic layer was driedover sodium sulfate, filtered and concentrated under reduced pressure.The crude product was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to affordN-[2-hydroxy-1-methoxy-6-oxo-2-(trifluoromethyl)-3H-pyridin-5-yl]benzamide(18 mmol, 6.0 g). ¹H NMR (400 MHz, CDCl₃) δ 8.68 (br s, 1H), 7.87-7.82(m, 2H), 7.59-7.47 (m, 4H), 4.35 (s, 1H), 3.95 (s, 3H), 3.11 (m, 1H),2.98 (m, 1H).

Step I1-B: Synthesis oftert-butyl-N-benzoyl-N-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]carbamate

To a 0° C. cooled solution ofN-[2-hydroxy-1-methoxy-6-oxo-2-(trifluoromethyl)-3H-pyridin-5-yl]benzamide(prepared in step I1-A, 9.1 mmol, 3.0 g) in dichloromethane (30 mL) wasadded N,N-diethylethanamine (18 mmol, 1.8 g, 2.5 mL) andN,N-dimethylpyridin-4-amine (1.8 mmol, 0.22 g). To this solution wasadded tert-butoxycarbonyl tert-butyl carbonate (23 mmol, 5.0 g). Thereaction was stirred for 18 hours at ambient temperature. The mixturewas diluted with water (20 ml) and extracted with dichloromethane (2×30ml). Combined organic layer was dried over sodium sulfate, filtered andconcentrated under reduced pressure. The crude product was purified bycombiflash (silica gel, 30% ethyl acetate-cyclohexane) to affordtert-butylN-benzoyl-N-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]carbamate(6.5 mmol, 2.7 g). ¹H NMR (400 MHz, CDCl₃) δ 7.87-7.75 (m, 2H),7.58-7.50 (m, 1H), 7.50-7.40 (m, 3H), 6.64 (d, 1H), 4.16 (s, 3H), 1.22(s, 9H).

Step I1-C: Synthesis oftert-butyl-N-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]carbamate

To a solutiontert-butyl-N-benzoyl-N-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]carbamate(1.212 mmol, 0.5 g) in tetrahydrofuran (5.0 mL) was added a solutionlithium hydroxide hydrate (1.819 mmol, 0.07631 g) in water (1.0 mL). Thereaction was stirred at ambient temperature for 4 hours. Then, thereaction was quenched with water (10 ml) and extracted with ethylacetate (3×30 ml). Combined organic layer was dried over sodium sulfate,filtered and concentrated under reduced pressure. The crude product waspurified by combiflash (silica gel, 30% ethyl acetate-cyclohexane) toafford tert-butylN-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]carbamate (1.071 mmol,0.33 g). ¹H NMR (400 MHz, CDCl₃) δ 7.96 (d, 1H), 7.76 (br s, 1H), 6.65(d, 1H), 4.15 (s, 3H), 1.52 (s, 9H).

Step I1-D: Synthesis of tert-butylN-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate

To a 0° C. cooled solution oftert-butyl-N-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]carbamate(6.2 mmol, 1.9 g) in tetrahydrofuran (20 mL) was added sodium hydride(9.2 mmol, 0.37 g). The reaction was stirred at same temperature for 30minutes. To this mixture was then added iodomethane (18 mmol, 2.6 g, 1.2mL). The reaction was allowed to warm up to ambient temperature over 1-2hours. Then, the reaction was diluted with water (15 ml), extracted withethyl acetate (3×20 ml). Combined organic layer was dried over sodiumsulfate, filtered and concentrated under reduced pressure. The crudeproduct was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to affordtert-butyl-N—[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate(5.6 mmol, 1.8 g). ¹H NMR (400 MHz, CDCl₃) δ 7.30 (d, 1H), 6.55 (d, 1H),4.16 (s, 3H), 3.18 (s, 3H), 1.46 (s, 9H).

Step I1-E: Synthesis of1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

To a solution oftert-butyl-N-[1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate(5.3 mmol, 1.7 g) in dichloromethane (20 mL) was added2,2,2-trifluoroacetic acid (26 mmol, 3.0 g, 2.0 mL). The reaction wasstirred at ambient temperature for 18 hours. The reaction was dilutedwith water (15 ml), neutralised with sodium bicarbonate solution,extracted with dichloromethane (3×20 ml). Combined organic layer wasdried over sodium sulfate, filtered and concentrated under reducedpressure. The crude product was purified by combiflash (silica gel, 30%ethyl acetate-cyclohexane) to afford1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (5.0 mmol,1.1 g). ¹H NMR (400 MHz, CDCl₃) δ 6.61 (d, 1H), 6.02 (d, 1H), 4.13 (s,3H), 2.89 (s, 3H).

Step I1-F: Synthesis of4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

To a 0° C. cooled solution of1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (5.0 mmol,1.1 g) in N,N-dimethylformamide (12 mL) was added N-bromosuccinimide(7.4 mmol, 1.3 g). The reaction was stirred for 1 hour. Then, thereaction was diluted with water (50 ml), extracted with ethyl acetate(3×30 ml). Combined organic layer was dried over sodium sulfate,filtered and concentrated under reduced pressure. The crude product waspurified by combiflash (silica gel, 20% ethyl acetate-cyclohexane) toafford4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one(0.6643 mmol, 0.2 g). ¹H NMR (400 MHz, CDCl₃) δ 6.70 (s, 1H), 4.11 (s,3H), 3.29 (s, 3H).

Example I2: Preparation of4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid (B4)

Step I2-A: Synthesis of methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate

To a solution of methyl 4-bromo-2-ethylsulfanyl-benzoate (WO2016/023954) (250 mg, 0.91 mmol) in dimethyl sulfoxide (8 mL) underargon were added water (4 mL), 4-isoxazoleboronic acid pinacol ester(213 mg, 1.09 mmol) and potassium fluoride (158 mg, 2.73 mmol). Thethick reaction mixture was purged with argon for 5 minutes, thenbis(triphenylphosphine)palladium(II) dichloride (6.4 mg, 0.009 mmol) wasadded. The vial was sealed and the mixture stirred in the microwave at90° C. for 40 minutes. The reaction mixture was poured into iced-water,the resulting yellowish suspension filtered and washed with cold water.This solid was dissolved in dichlormethane, the solution dried oversodium sulfate and reduced to dryness under vacuum to afford methyl2-ethylsulfanyl-4-isoxazol-4-yl-benzoate as a yellowish solid. Thismaterial was used in the next step without further purification. LCMS(method A): 262 (M−H)—, retention time 0.88 min.

Step I2-B: Synthesis of methyl 4-(cyanomethyl)-2-ethylsulfanyl-benzoate

To a solution of methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate (760mg, 2.89 mmol) in methanol (15 mL) was added a 1M potassium fluoridesolution in water (8.66 mL, 8.66 mmol). The reaction mixture was stirredat reflux for 3 hours. After cooling, the suspension was filtered andthe filtrate concentrated to dryness in vacuo. The residue was purifiedby Combiflash over silicagel to afford methyl4-(cyano-methyl)-2-ethylsulfanyl-benzoate as a gum. LCMS (method A): 236(M+H)⁺, retention time 0.90 min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.42 (t,3H), 2.99 (q, 2H), 3.80 (s, 2H), 3.93 (s, 3H), 7.10 (dd, 1H), 7.28 (d,1H), 7.99 (d, 1H).

Step I2-C: Synthesis of methyl4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate (B3)

To a solution of methyl 4-(cyano-methyl)-2-ethylsulfanyl-benzoate (300mg, 1.275 mmol) in acetonitrile (15 mL) were added cesium carbonate(1.24 g, 3.825 mmol) and 1,2-dibromoethane (719 mg, 3.825 mmol). Thereaction mixture was stirred at reflux for 90 minutes. After cooling,the suspension was filtered and the filtrate concentrated to dryness invacuo. The residue was purified by Combiflash over silicagel to affordmethyl 4-(cyano-methyl)-2-ethylsulfanyl-benzoate as an oil. LCMS (methodA): 262 (M+H)⁺, retention time 0.98 min. ¹H NMR (400 MHz, CDCl₃) δ ppm1.43 (t, 3H), 1.48 (m, 2H), 1.82 (m, 2H), 3.01 (q, 2H), 3.92 (s, 3H),6.88 (dd, 1H), 7.35 (d, 1H), 7.94 (d, 1H).

Step I2-D: Synthesis of 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate(B4)

To a solution of methyl 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate(198 mg, 0.758 mmol) in a mixture of tetrahydrofuran (9 mL) and water (3mL) at 0-5° C. was added lithium hydroxide (1.5 eq., 1.137 mmol) and thereaction mixture was stirred at room temperature overnight. The solutionwas concentrated in vacuo, the residue diluted with t-butyl methyl ether(10 mL) and acidified with a 1M aqueous hydrochloric acid solution (10mL). The organic layer was separated, the aqueous layer extracted witht-butyl methyl ether, the combined organic layers washed with water andbrine, dried over sodium sulfate, filtered and concentrated underreduced pressure to afford4-(1-cyano-cyclopropyl)-2-ethylsulfanyl-benzoate as a solid. Thismaterial was used in the next step without further purification. LCMS(method A): 246 (M−H)—, retention time 0.83 min. ¹H NMR (400 MHz, CDCl₃)δ ppm 1.44 (t, 3H), 1.51 (m, 2H), 1.85 (m, 2H), 3.03 (q, 2H), 6.90 (dd,1H), 7.41 (d, 1H), 8.10 (d, 1H).

Example I3: Preparation of5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid(B6)

Step I3-A: Synthesis of methyl5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (B5)

To a solution of methyl5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (4.0 g, 16.93mmol) in acetonitrile (135 mL) were added cesium carbonate (16.55 g,50.78 mmol) and methyl iodide (4.805 g, 33.86 mmol). The reactionmixture was stirred at 80° C. for 3 hours. After cooling, the mixturewas diluted with water (15 mL) and the product extracted with ethylacetate (3×10 mL). The combined organic layers were washed with brine,dried over sodium sulfate, filtered and concentrated under reducedpressure. The crude product was purified by combiflash (silica gel, 20%ethyl acetate-cyclohexane) to afford methyl5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (B5)(2.3 g, 8.70 mmol). LCMS (method E): 265 (M+H)⁺, retention time 0.91min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.44 (t, 3H), 1.81 (s, 6H), 3.02 (q,2H), 4.03 (s, 3H), 7.87 (d, 1H), 8.52 (d, 1H).

Step I3-B: Synthesis of5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid(B6)

To a solution of methyl5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (B5)(2.25 g, 8.51 mmol) in tetrahydrofuran (15 mL) were added lithiunhydroxide monohydrate (714 mg, 17.0 mmol) and water (5 mL) and thereaction mixture was stirred at room temperature for 5 hours. Thesolution was concentrated in vacuo, the residue diluted with water (20mL) and acidified with a 2M aqueous hydrochloric acid solution (5 mL).The aqueous layer was extracted with ethyl acetate (7×20 mL), thecombined organic layers washed with brine, dried over sodium sulfate,filtered and concentrated under reduced pressure to afford5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid(B6) as a solid. This material was used in the next step without furtherpurification. LCMS (method E): 251 (M+H)⁺, retention time 0.78 min. ¹HNMR (400 MHz, d6-DMSO) δ ppm 1.26 (t, 3H), 1.77 (s, 6H), 3.04 (q, 2H),7.84 (d, 1H), 8.53 (d, 1H).

Example I4: Preparation of4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoic acid (B8)

Step I4-A: Synthesis of methyl4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoate (B7)

To a solution of methyl 4-(cyanomethyl)-2-ethylsulfanyl-benzoate (120mg, 0.510 mmol) in N,N-dimethylformamide (4 mL) at 0° C. was addedsodium hydride (49 mg, 1.224 mmol, 60%) and the mixture was stirred for30 minutes. Methyl iodide (76.2 μL, 173.7 mg, 1.224 mmol) was furtheradded and stirring continued at room temperature for 2 hours. Aftercooling, the mixture was diluted with water (10 mL) and the productextracted with ethyl acetate (3×20 mL). The combined organic layers werewashed with brine, dried over sodium sulfate, filtered and concentratedunder reduced pressure. The crude product was co-evaporated with toluene(2-3 times) to afford methyl4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoate (B7). ¹H NMR (400MHz, CDCl₃) δ=1.43 (t, 3H), 1.75 (s, 6H), 3.02 (q, 2H), 3.93 (s, 3H),7.20 (dd, 1H), 7.46 (d, 1H), 7.99 (m, 1H).

Step I4-B: Synthesis of4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoic acid (B8)

Obtained from methyl 4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoate(B7) (760 mg, 2.77 mmol), lithium hydroxide monohydrate (4.15 mmol) intetrahydrofuran (20 mL) and water (6 mL) according to procedure ExampleI3, step 13-B. The mixture was stirred at room temperature for twohours, then concentrated under reduced pressure. The crude materialobtained after extractive workup was thoroughly dried in vacuo to afford4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoic acid (B8) as a solid.This material was used in the next step without further purification.LCMS (method E): 250 (M+H)⁺, retention time 0.76 min.

b) Synthesis of Examples of Compounds of Formula (I) Example P1:Preparation of2-(3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A2)

Step P1-A: Synthesis ofN-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide

To a 0° C. cooled solution of 3-ethylsulfanylpyridine-2-carboxylic acid(commercially available, CAS 14440-97-2, 2.183 mmol, 0.4 g) indichloromethane (78 mmol, 6.6 g, 5.0 mL) and DMF (1 drop) was addedoxalyl dichloride (3.93 mmol, 0.4988 g, 0.34 mL). The reaction wasstirred for 2-3 hours and was concentrated under reduced pressure toremove all volatiles. Dichloromethane (5 mL) was added to this acidchloride. In an flask was taken4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl) pyridin-2-one(1.587 mmol, 0.4777 g), N,N-diethylethanamine (5.95 mmol, 0.6021 g, 0.82mL) in dichloromethane (5.0 mL) and cooled to 0° C. Then, to thismixture was added the solution of 3-ethylsulfanylpyridine-2-carbonylchloride (1.983 mmol, 0.4 g) in dichloromethane (5 ml) prepared before.The reaction mass was stirred at ambient temperature for 2 hours. Thenthe reaction was diluted with water (15 ml), extracted withdichloromethane (3×20 ml). Combined organic layer was dried over sodiumsulfate, filtered and concentrated under reduced pressure. The crude waspurified by combiflash (silica gel, 30% ethyl acetate-cyclohexane) toaffordN-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(0.5361 mmol, 0.25 g). ¹H NMR (400 MHz, CDCl₃) δ 7.93 (m, 1H), 7.62 (d,1H), 7.16 (m, 1H), 6.58 (s, 1H), 4.09 (s, 3H), 3.37 (s, 3H), 2.94 (m,2H), 1.37 (t, 3H).

Step P1-B: Synthesis ofN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide

To a solution ofN-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(0.5361 mmol, 0.25 g) in N,N-dimethylformamide (3.0 mL) was added sodiumazide (1.608 mmol, 0.1046 g). The reaction was heated at 90° C. for 3hours. Then, the mixture was diluted with water (15 ml), extracted withethyl acetate (3×30 ml). Combined organic layer was dried over sodiumsulfate, filtered and concentrated under reduced pressure. The crudeproduct was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to affordN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(0.2556 mmol, 0.11 g). ¹H NMR (400 MHz, CDCl₃) δ 8.03 (m, 1H), 7.63 (d,1H), 7.16 (m, 1H), 6.14 (s, 1H), 3.98 (s, 3H), 3.35 (s, 3H), 2.96 (m,2H), 1.37 (t, 3H).

Step P1-C: Synthesis of2-(3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A1)

To a microwave vial charged withN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(0.233 mmol, 0.1 g) in dry toluene (2.0 mL) was added triphenylphosphane(0.233 mmol, 0.0612 g). The reaction mixture was stirred at ambienttemperature for 2 hours, then subjected to microwave heating at 150° C.for 2 hours. The reaction was diluted with water (10 ml), extracted withethyl acetate (3×20 ml). Combined organic layer was dried over sodiumsulfate, filtered and concentrated under reduced pressure. The crudeproduct was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to afford2-(3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (0.1041 mmol, 0.04 g). ¹H NMR (400 MHz,CDCl₃) δ 8.52 (br d, 1H), 7.78 (d, 1H), 7.40 (dd, 1H), 7.20 (s, 1H),4.20 (m, 6H), 2.95 (q, 2H), 1.34 (t, 3H).

Step P1-D: Synthesis of2-(3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A2)

To a solution of2-(3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(0.0780 mmol, 0.03 g) in dichloromethane (2.0 mL) was addedmeta-chloroperoxybenzoic acid (0.172 mmol, 0.0423 g). The reaction wasstirred at ambient temperature for 18 hours. The reaction mass wasquenched with an aqueous sodium bicarbonate solution (20 ml), extractedwith dichloromethane (3×20 ml). The combined organic layer was driedover sodium sulfate, filtered and concentrated under reduced pressure.The crude product was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to afford2-(3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoro-methyl)imidazo[4,5-c]pyridin-4-one (0.0480 mmol, 0.02 g). ¹H NMR (400 MHz,CDCl₃) δ 9.00 (d, 1H), 8.52 (d, 1H), 7.73 (m, 1H), 7.09 (s, 1H), 4.21(s, 3H), 4.08 (s, 3H), 3.74 (q, 2H), 1.35 (t, 3H).

Example P2: Preparation of2-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A3)

Step P2-A: Synthesis of2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A10)

To a solution of2-(3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A1) (600 mg, 1.56 mmol) indichloromethane (30 mL) was added meta-chloroperoxybenzoic acid (1.92 g,7.80 mmol), and the mixture was heated at reflux overnight. The reactionmixture was quenched with an aqueous sodium bicarbonate solution (20 ml)and extracted with dichloromethane (3×20 ml). The combined organiclayers were dried over sodium sulfate, filtered and concentrated underreduced pressure. The crude product was purified by combiflash (silicagel, 80% ethyl acetate-cyclohexane) to afford2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A10) as a solid (0.925 mmol, 400 mg). LCMS (method D): 433(M+H)⁺, retention time 1.29 min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.37 (t,3H), 3.45 (m, 1H), 3.72 (m, 1H), 4.04 (s, 3H), 4.20 (s, 3H), 7.11 (s,1H), 7.68 (t, 1H), 7.97 (d, 1H), 8.53 (d, 1H).

Step P2-B: Synthesis of2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A11)

A solution of2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A10) (800 mg, 1.85 mmol) inphosphorus oxychloride (8 mL) was heated at 110° C. for 45 minutes. Thereaction mixture was poured into crushed ice (10 g) and neutralised withsolid sodium bicarbonate. The aqueous layer was extracted withdichloromethane (3×10 ml), the combined organic layers dried over sodiumsulfate, filtered and concentrated under reduced pressure. The crudeproduct was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to afford2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A11) as a solid (1.24 mmol, 0.56 g). LCMS (method D): 451/453(M+H)⁺, retention time 1.49 min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.36 (t,3H), 3.76 (q, 2H), 4.12 (s, 3H), 4.20 (s, 3H), 7.09 (s, 1H), 7.72 (d,1H), 8.45 (d, 1H).

Step P2-C: Synthesis of2-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A3)

To a solution of2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A11) (500 mg, 1.11 mmol) inN,N-dimethylformamide (20 mL) was added potassium carbonate (155.5 mg,1.11 mmol), followed by 1H-1,2,4-triazole (76.6 mg, 1.11 mmol) and themixture was stirred at room temperature for 3 hours. The reactionmixture was diluted with water (30 ml), extracted with ethyl acetate(3×50 ml), the combined organic layers dried over sodium sulfate,filtered and concentrated under reduced pressure. The crude product waspurified by combiflash (silica gel, 40% ethyl acetate-cyclohexane) toafford2-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A3) as a solid (0.81 mmol, 390 mg), mp 227-229° C. LCMS(method D): 484 (M+H)⁺, retention time 1.42 min. ¹H NMR (400 MHz, CDCl₃)δ ppm 1.37 (t, 3H), 3.73 (q, 2H), 4.12 (s, 3H), 4.22 (s, 3H), 7.12 (s,1H), 8.20 (s, 1H), 8.30 (d, 1H), 8.69 (d, 1H), 9.15 (s, 1H).

Example P3: Preparation of2-(6-amino-5-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A14)

Step P3-A: Synthesis of2-(6-amino-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A13)

A pressure vessel was charged with a solution of2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A11) (460 mg, 1.02 mmol) in tetrahydrofuran (7 mL). A 30%aqueous solution of ammonium hydroxide (8 mL, 62.3 mmol, 30%) was added,the vessel sealed and heated to 100° C. for 3 hours. The reactionmixture was concentrated in vacuo, the residue diluted with water andthe product extracted with dichloromethane. The combined organic layerswere washed with water and brine, dried over sodium sulfate, filteredand concentrated under reduced pressure. The crude product was purifiedby combiflash (silica gel, 40% ethyl acetate-cyclohexane) to afford2-(6-amino-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A13) as a solid (0.60 mmol, 257mg), mp 210-212° C. LCMS (method E): 432 (M+H)⁺, retention time 0.76min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.23 (t, 3H), 3.44 (q, 2H), 3.97 (s,3H), 4.12 (s, 3H), 5.12 (br s, 2H), 6.64 (d, J=8.80 Hz, 1H), 7.00 (s,1H), 8.04 (d, J=8.80 Hz, 1H).

Step P3-B: Synthesis of2-(6-amino-5-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A14)

To a solution of2-(6-amino-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound A13) (100 mg, 0.232 mmol) in dryN,N-dimethylformamide (3 mL) was added N-chlorosuccinimide (0.9 eq.,0.209 mmol) and reaction mixture was stirred at 45° C. for 3 hours. Thereaction mixture was diluted with water, extracted with ethyl acetate,the combined organic layers washed with water and brine, dried oversodium sulfate, filtered and concentrated under reduced pressure. Thecrude product was purified by combiflash (silica gel, 30% ethylacetate-cyclohexane) to afford2-(6-amino-5-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoro-methyl)imidazo[4,5-c]pyridin-4-one(title compound A14) as a solid (0.118 mmol, 55 mg), mp 211-213° C. LCMS(method E): 466/468 (M+H)⁺, retention time 0.96 min. ¹H NMR (400 MHz,CDCl₃) δ ppm 1.25 (t, 3H), 3.50 (q, 2H), 3.97 (s, 3H), 4.11 (s, 3H),5.53 (br s, 2H), 7.00 (s, 1H), 8.14 (s, 1H).

Example P4: Preparation of1-[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compoundA8)

Step P4-A: Preparation of methyl5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate

Methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (1 g, 3.62 mmol)was dissolved in dry dimethyl sulfoxide (10 mL). Dipotassium carbonate(1.25 g, 9.05 mmol) and benzyl(triethyl)ammonium chloride (8 mg, 0.036mmol) were added to the stirred solution, followed by the slow additionof ethyl 2-cyanoacetate (0.614 g, 5.43 mmol). The resulting mixture washeated to 90° C. for 3 hours. The reaction mixture was cooled to roomtemperature, diluted with ethyl acetate (20 mL) and slowly treated withan aqueous 2 M hydrochloric acid solution (5 mL) and water (20 mL). Theaqueous layer was extracted with ethyl acetate (2×20 mL). The combinedorganic layers were dried (Na₂SO₄), filtered, and concentrated underreduced pressure. The crude compound was purified by chromatography oversilica gel (80% ethyl acetate in cyclohexane). The resulting materialwas dried under a high vacuum for several hours to afford the desiredmethyl5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate(705 mg). LCMS (method E): 309 (M+H)⁺, retention time 0.93 min. ¹H NMR(400 MHz, CDCl₃) δ ppm 1.32 (t, 3H), 1.43 (t, 3H), 3.00 (q, 2H), 4.03(s, 3H), 4.30 (q, 2H), 7.83 (d, 1H), 8.49 (d, 1H).

Step P4-B: Preparation of methyl5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate

Methyl5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate(0.700 g, 2.27 mmol) was dissolved in dimethyl sulfoxide (10 mL) andsodium chloride (1.32 g, 22.70 mmol) which was dissolved in a minimumamount of water (5 mL) was added to this solution. The resulting orangereaction mixture was heated to 120-130° C. After 5 hours, the mixturewas cooled to 25° C., diluted with ethyl acetate (20 mL), and washedsuccessively with water (20 mL) and brine (10 mL). The combined organiclayer was dried (Na₂SO₄), filtered, and concentrated under reducedpressure. The crude was purified by chromatography over silica gel (50%ethyl acetate in cyclohexane) to afford methyl5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (0.470 g). LCMS(method E): 237 (M+H)⁺, retention time 0.84 min. ¹H NMR (400 MHz, CDCl₃)δ ppm 1.44 (t, 3H), 3.01 (q, 2H), 3.90 (s, 2H), 4.04 (s, 3H), 7.77 (d,1H), 8.43 (d, 1H).

Step P4-C: Preparation of methyl5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate (B1)

To a solution of methyl5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (0.470 g, 1.99mmol) in acetonitrile (16 mL) were added cesium carbonate (1.94 g, 5.97mmol) and 1,2-dibromoethane (0.346 mL, 3.98 mmol). The brown solutionwas stirred at 80° C. for 3 hours. The reaction mixture was cooled toroom temperature and poured into water (15 mL). The aqueous layer wasextracted 3 times with ethyl acetate (each 10 mL). The combined organiclayers were washed once with brine (20 mL) and dried over Na2SO₄,filtered and concentrated under reduced pressure. The crude product waspurified by chromatography over silica gel (60% ethyl acetate incyclohexane) to afford methyl5-(1-cyano-cyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate (0.455 g,B1). LCMS (method E): 263 (M+H)⁺, retention time 0.87 min. ¹H NMR (400MHz, CDCl₃) δ ppm 1.46 (t, 3H), 1.63 (m, 2H), 1.96 (m, 2H), 3.03 (q,2H), 4.04 (s, 3H), 7.87 (d, 1H), 8.20 (d, 1H).

Step P4-D: Preparation of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (B2)

To a solution of methyl5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate (B1, 450mg, 1.716 mmol) in methanol (6 mL) were added lithium hydroxidemonohydrate (3.431 mmol) and water (1 mL). The reaction mixture wasstirred at room temperature for 2 hours, then concentrated to drynessunder reduced pressure. The residue was diluted with water (5 mL) andacidified with an aqueous 2N hydrochloric acid solution (5-10 mL). Theaqueous layer was extracted with ethyl acetate (3×20 mL), the combinedorganic layers dried over sodium sulfate, filtered and concentratedunder reduced pressure to afford pure5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (B2)(370 mg, 1.490 mmol) as a solid. This material was used in the next stepwithout further purification. LCMS (method E): 249 (M+H)⁺, retentiontime 0.69 min. ¹H NMR (400 MHz, d6-DMSO) δ ppm 1.26 (t, 3H), 1.74 (m,2H), 1.86 (m, 2H), 3.03 (q, 2H), 7.63 (d, 1H), 8.36 (d, 1H).

Step P4-E: Preparation ofN-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide

To a solution of4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one(Example I1, step I1-F) (5.0 g, 16.61 mmol) in dichloromethane (100 mL)was added trifluoroacetic anhydride (7.09 mL, 49.82 mmol) at roomtemperature. The reaction mixture was stirred for 30 minutes at roomtemperature and then evaporated to dryness under reduced pressure. Water(100 mL), then an aqueous saturated potassium carbonate solution (50 mL)were added and the aqueous layer was extracted with ethyl acetate (100mL). The organic layer was washed with brine (100 mL), dried over sodiumsulfate, filtered and concentrated. The crude product was purified oversilica gel to afford pureN-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide.

This material was used in the next step without further purification.LCMS (method E): 397/399 (M+H)⁺, retention time 0.96 min. ¹H NMR (400MHz, CDCl₃) δ ppm 3.27 (s, 3H), 4.16 (s, 3H), 6.84 (s, 1H).

Step P4-F: Preparation ofN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide

To a solution ofN-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide(11.8 g, 29.7 mmol) in N,N-dimethylformamide (110 mL) was added sodiumazide (2.9 g, 44.6 mmol) at room temperature. The reaction mixture wasstirred at room temperature overnight. The above reaction was separatelyduplicated, then the combined mixtures were diluted with cold water (500mL) and extracted with ethyl acetate (3×150 mL). The combined organiclayers were washed with water (100 mL) and brine, dried over sodiumsulfate, filtered and concentrated under reduced pressure below 40° C.to affordN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide.This material was used in the next step without further purification.LCMS (method E): 360 (M+H)+, retention time 0.90 min. ¹H NMR (400 MHz,CDCl₃) δ ppm 3.23 (s, 3H), 4.15 (s, 3H), 6.40 (s, 1H).

Step P4-G: Preparation of4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

To a solution ofN-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide(4.6 g, 13.0 mmol) in methanol (100 mL) was added potassium carbonate(4.7 g, 33.0 mmol). The reaction mixture was stirred at room temperatureovernight, then diluted with water (150 mL). The aqueous layer wasextracted with ethyl acetate (2×75 mL), the combined organic layerswashed with brine (150 mL), dried over sodium sulfate, filtered andconcentrated under reduced pressure. The crude product was purified onsilica gel (40% ethyl acetate in cyclohexane) to afford4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (2.2g, 8.4 mmol). LCMS (method E): 264 (M+H)⁺, retention time 0.94 min. ¹HNMR (400 MHz, CDCl₃) δ ppm 3.18 (s, 3H), 4.11 (s, 3H), 6.46 (s, 1H).

Step P4-H: Preparation of4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

To a solution of4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (1.7g, 6.5 mmol) in tetrahydrofuran (50 mL) and water (5 mL) at roomtemperature was added triphenylphosphine (5.1 g, 19 mmol) and theresulting mixture stirred at room temperature for 2 hours. A 2M aqueoushydrochloric acid solution (9 mL, 18 mmol, 2 mol/L) was added andstirring continued overnight at room temperature. The reaction mixturewas concentrated and quenched using an aqueous saturated potassiumcarbonate solution (20 mL). The aqueous layer was extracted with ethylacetate (2×75 mL), the combined organic layers washed with brine (100mL), dried over sodium sulfate, filtered and concentrated under reducedpressure. The residue was purified on silica gel (50-60% ethyl acetatein cyclohexane) to afford4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one. LCMS(method E): 238 (M+H)⁺, retention time 0.18 min. ¹H NMR (400 MHz,d6-DMSO) δ ppm 2.60 (s, 3H), 3.98 (s, 3H), 5.75 (s, 2H), 6.42 (s, 1H).

Step P4-I: Preparation of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(Isomeric Mixture)

To a suspension of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (B2)(400 mg, 1.61 mmol) in dichloromethane (16 mL) were added a catalyticamount of N,N-dimethylformamide (2 drops) and oxalyl chloride (3.22mmol, 0.287 mL) dropwise. The reaction was stirred at room temperaturefor 6 hours and the solvent was removed in vacuo to afford5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride.

A solution of above5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (428mg, 1.60 mmol) in dry tetrahydrofuran (20 mL) was added slowly to amixture of4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one(456.6 mg, 1.92 mmol) and triethylamine (0.678 mL, 4.81 mmol) intetrahydrofuran (9.6 mL). The reaction mixture was stirred at roomtemperature for 2 hours, then quenched with water and extracted withdichloromethane (100 ml). The combined organic layers were washed withwater and brine, dried with anhydrous sodium sulfate and concentratedunder reduced pressure to afford the desired isomeric mixture of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(750 mg, 1.60 mmol). This material was used in the next step withoutfurther purification. LCMS (method E): 468 (M+H)⁺, retention time 0.86min.

Step P4-J: Preparation of 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (A 18)

A solution of above isomeric mixture of5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(750 mg, 1.60 mmol) in acetic acid (4.8 mL) was heated to 100° C. for 48hours. After cooling to room temperature, the reaction mixture wasevaporated. The residue was poured into water and extracted with ethylacetate (3×100 mL), the combined organic layers washed with brine, driedover sodium sulfate and evaporated under reduced pressure. The crudeproduct was purified by chromatography on silica gel (40% ethyl acetatein cyclohexane) to afford the desired product1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(350 mg) as a solid. LCMS (method E): 450 (M+H)⁺, retention time 1.03min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.37 (t, 3H), 1.59 (m, 2H), 1.93 (m,2H), 3.01 (q, 2H), 4.20 (s, 3H), 4.21 (s, 3H), 7.25 (s, 1H), 7.76 (d,J=2.0 Hz, 1H), 8.32 (d, J=2.0 Hz, 1H).

Step P4-K: Synthesis of1-[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(compound A8)

To a solution of 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(190 mg, 0.423 mmol) in dichloromethane (15 mL) at 0-5° C. was addedmeta-chloroperoxybenzoic acid (214 mg, 0.930 mmol, 75%) and the mixturewas stirred for 2 hours. The reaction mixture was quenched with anaqueous sodium bicarbonate solution and extracted with dichloromethane(3×50 mL). The combined organic layers were washed with water and brine,dried over anhydrous sodium sulfate and concentrated under reducedpressure. The residue was purified by chromatography on silica gel (50%ethyl acetate in cyclohexane) to afford the desired product1-[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile(compound A8) as a solid (121 mg), mp 188-190° C. LCMS (method E): 482(M+H)⁺, retention time 0.97 min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.37 (t,3H), 1.67 (m, 2H), 2.05 (m, 2H), 3.80 (q, 2H), 4.08 (s, 3H), 4.21 (s,3H), 7.09 (s, 1H), 8.23 (d, J=2.3 Hz, 1H), 9.03 (d, J=2.3 Hz, 1H).

Example P5: Preparation of2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A17)

Step P5-A: Preparation of5-bromo-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-bromo-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(isomeric mixture)

5-Bromo-3-ethylsulfanyl-pyridine-2-carbonyl chloride was obtained from5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid (WO 2016/005263) (300mg, 1.145 mmol), a catalytic amount of N,N-dimethylformamide (0.01 mL)and oxalyl chloride (1.373 mmol, 0.121 mL) in dichloromethane (15 mL)according to procedure Example P4, Step P4-I. The reaction was stirredat room temperature for 1.5 hours and the solvent was removed in vacuo.

The isomeric mixture of5-bromo-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoro-methyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-bromo-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamidewas obtained from above 5-bromo-3-ethylsulfanyl-pyridine-2-carbonylchloride (1.145 mmol),4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (407mg, 1.717 mmol) and diisopropylethylamine (0.797 mL, 4.58 mmol) intetrahydrofuran (20 mL) according to procedure Example P4, Step P4-I.The reaction mixture was stirred at room temperature for 3 hours, pouredinto an aqueous saturated potassium carbonate solution (10 mL) and water(100 mL), and extracted with ethyl acetate (50 mL). The organic layerwas washed with brine (20 mL), dried over anhydrous sodium sulfate andconcentrated under reduced pressure. The residue was purified bychromatography on silica gel (40% ethyl acetate in cyclohexane) toafford the isomeric products (392 mg). LCMS (method E): 481/483 (M+H)⁺,retention time 0.93 min.

Step P5-B: Preparation of2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(A19)

Obtained from above isomeric mixture of5-bromo-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamideandN-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-bromo-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide(300 mg, 0.623 mmol) in acetic acid (1.9 mL) according to procedureExample P4, Step P4-J. The reaction mixture was heated to 100° C. for 24hours. The residue from the extractive workup was purified bychromatography on silica gel (40% ethyl acetate in cyclohexane) toafford2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-oneas a solid (270 mg), mp 167-169° C. LCMS (method E): 463/465 (M+H)⁺,retention time 1.11 min. ¹H NMR (400 MHz, CDCl₃) δ ppm 1.37 (t, 3H),2.98 (q, 2H), 4.20 (s, 3H), 4.22 (s, 3H), 7.25 (s, 1H), 7.87 (d, J=1.9Hz, 1H), 8.55 (d, J=1.9 Hz, 1H).

Step P5-C: Synthesis of2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A17)

Obtained from2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-trifluoromethyl)imidazo[4,5-c]pyridin-4-one(130 mg, 0.281 mmol) and meta-chloroperoxybenzoic acid (142 mg, 0.617mmol, 75%) in dichloromethane (15 mL) according to procedure Example P4,Step P4-K. The residue from the extractive workup was purified bychromatography on silica gel (30% ethyl acetate in cyclohexane) toafford2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one(compound A17) as a solid (88 mg), mp 173-175° C. LCMS (method E):495/497 (M+H)⁺, retention time 1.03 min. ¹H NMR (400 MHz, CDCl₃) δ ppm1.38 (t, 3H), 3.80 (q, 2H), 4.09 (s, 3H), 4.20 (s, 3H), 7.09 (s, 1H),8.64 (d, J=2.2 Hz, 1H), 9.04 (d, J=2.2 Hz, 1H).

TABLE A This table discloses compounds of the formula I-2d: (I-2d)

Comp. No. X R₃ R₆ A Analytical data & IUPAC name A1  S H H N Seepreparatory examples (1.001) 2-(3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c] pyridin-4-one A2  SO₂ H H N Seepreparatory examples (1.002) 2-(3-ethylsulfonyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c] pyridin-4-one A18 S

H N LCMS (method E): 450 (M + H)⁺, retention time 1.03 min.1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile A19 S Br H N LCMS (method E):463/465 (M + H)⁺, retention time 1.11 min.2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl) imidazo[4,5-c]pyridin-4-one A20 S HCl N LCMS (method E): 419/421 (M + H)⁺, retention time 1.11 min.2-(6-chloro-3-ethylsulfanyl-2-pyridyl)-5-methoxy-3-methyl-6-(trifluoromethyl) imidazo[4,5-c]pyridin-4-one A21 SCF₃ H N LCMS (method D): 453 (M + H)⁺, retention time 1.56 min.2-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-5-methoxy-3-methyl-6-(trifluoromethyl) imidazo[4,5-c]pyridin-4-one A22 SH H CH LCMS (method E): 384 (M + H)⁺, retention time 1.08 min.2-(2-ethylsulfanylphenyl)-5-methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one A23 S

H CH LCMS (method A): 449 (M + H)⁺, retention time 1.03 min.1-[3-ethylsulfanyl-4-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile A24 S

H N LCMS (method E): 452 (M + H)⁺, retention time 1.05 min.2-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile A25 S

H CH LCMS (method E): 451 (M + H)⁺, retention time 1.12 min.2-[3-ethylsulfanyl-4-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]-2-methyl-propanenitrile Further examples of compounds offormula (I), respectively of formula (I-2d) wherein A, X, R₃ and R₆ areas structurally drawn LCMS R_(t) [M + H]⁺ MP No. IUPAC name Structures(min) (measured) Method (° C.) A3  2-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-5- methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-4-one

1.42 484 D 220- 223 A4  2-[3-ethylsulfonyl-6-(triazol-1-yl)-2-pyridyl]-5-methoxy-3- methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one

0.97 484 E 166- 168 A5  2-[3-ethylsulfonyl-6-(triazol-2-yl)-2-pyridyl]-5-methoxy-3- methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one

0.96 484 E 180- 182 A6  2-[3-ethylsulfonyl-5-(trifluoro-methyl)-2-pyridyl]-5-methoxy- 3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one

1.05 485 E 158- 160 A7  2-(2-ethylsulfonylphenyl)-5- methoxy-3-methyl-6-(trifluoro- methyl)imidazo[4,5-c] pyridin-4- one

1.36 416 D 166- 168 A8  1-[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl] cyclopropanecarbonitrile

0.97 482 E 188- 190 A9  1-[3-ethylsulfonyl-4-[5-methoxy-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl] cyclopropanecarbonitrile

0.94 481 A 212- 214 A10 2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-5-methoxy- 3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one

1.29 433 D solid A11 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3- methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one

1.49 451/453 D 195- 197 A12 2-[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2- methyl-propanenitrile

1.00 484 E 191- 193 A13 2-(6-amino-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3- methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one

0.76 432 E 210- 212 A14 2-(6-amino-5-chloro-3-ethylsulfonyl-2-pyridyl)-5- methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-4-one

0.96 466/468 E 211- 213 A15 2-[3-ethylsulfonyl-4-[5-methoxy-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]-2- methyl- propanenitrile

1.02 483 E 164- 166 A16 2-(6-amino-5-bromo-3-ethylsulfonyl-2-pyridyl)-5- methoxy-3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-4-one

0.99 510/512 E 214- 216 A17 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-methoxy-3- methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one

1.03 495/497 E 173- 175

TABLE B Examples of intermediates of formula (II), (IIb), repectively(II-4), (II-6), (II-7) and (II-8) LCMS [M + H]⁺ No. IUPAC nameStructures R_(t) (min) (measured) Method MP (° C.) B1 methyl5-(1-cyanocyclopropyl)- 3-ethylsulfanyl-pyridine-2- carboxylate

0.87 263 E — B2 5-(1-cyanocyclopropyl)-3- ethylsulfanyl-pyridine-2-carboxylic acid

0.69 249 E solid B3 methyl 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate

0.98 262 A — B4 4-(1-cyanocyclopropyl)-2- ethylsulfanyl-benzoic acid

0.83 246 [M − H]⁻ A solid B5 methyl 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine- 2-carboxylate

0.91 265 E — B6 5-(1-cyano-1-methyl-ethyl)-3- ethylsulfanyl-pyridine-2-carboxylic acid

0.78 251 E solid B7 methyl 4-(1-cyano-1-methyl-ethyl)-2-ethylsulfanyl-benzoate

¹H NMR (400 MHz, CDCl₃) δ = 1.43 (t, 3H)), 1.75 (s, 6H), 3.02 (q, 2H),3.93 (s, 3H), 7.20 (dd, 1H), 7.46 (d, 1H), 7.99 (m, 1H). B84-(1-cyano-1-methyl-ethyl)-2- ethylsulfanyl-benzoic acid

0.76 250 E solid

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use. Suitable additions to active ingredients here are,for example, representatives of the following classes of activeingredients: organophosphorus compounds, nitrophenol derivatives,thioureas, juvenile hormones, formamidines, benzophenone derivatives,ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinatedhydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides,neonicotinoids and Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds described in Table 1and A of the present invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (628)+TX, an acaricide selected from the group ofsubstances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPACname) (910)+TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/ChemicalAbstracts name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide(IUPAC name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name)(981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX,acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX,alpha-cypermethrin (202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX,amidothioate (872)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, aramite (881)+TX, arsenous oxide (882)+TX,AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX,azocyclotin (46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos[CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name) [CCN]+TX,bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate+TX, bromocyclen (918)+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin (99)+TX,butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX,carbophenothion (947)+TX, CGA 50′439 (development code) (125)+TX,chinomethionat (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX,chlordimeform hydrochloride (964)+TX, chlorfenapyr (130)+TX,chlorfenethol (968)+TX, chlorfenson (970)+TX, chlorfensulfide (971)+TX,chlorfenvinphos (131)+TX, chlorobenzilate (975)+TX, chloromebuform(977)+TX, chloromethiuron (978)+TX, chloropropylate (983)+TX,chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos(994)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX,clofentezine (158)+TX, closantel [CCN]+TX, coumaphos (174)+TX,crotamiton [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX,cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX,cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM(1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O (1037)+TX,demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX,demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos+TX, dicofol(242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081)+TX,dimethoate (262)+TX, dinactin (653)+TX, dinex (1089)+TX, dinex-diclexine(1089)+TX, dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX,dinocap-6 [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon(1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone(IUPAC name) (1103)+TX, disulfiram [CCN]+TX, disulfoton (278)+TX, DNOC(282)+TX, dofenapyn (1113)+TX, doramectin [CCN]+TX, endosulfan (294)+TX,endothion (1121)+TX, EPN (297)+TX, eprinomectin [CCN]+TX, ethion(309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos(1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide(330)+TX, fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad+TX,fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil (1161)+TX,fenvalerate (349)+TX, fipronil (354)+TX, fluacry-pyrim (360)+TX,fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron (366)+TX,flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron (370)+TX,flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC1137 (development code) (1185)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptenophos(432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstractsname) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name)(542)+TX, isocarbophos (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX,jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, malathion(492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX,mesulfen [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX,methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methylbromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX, mexacarbate(1290)+TX, milbemectin (557)+TX, milbemycin oxime [CCN]+TX, mipafox(1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin[CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512 (compoundcode)+TX, nifluridide (1309)+TX, nikkomycins [CCN]+TX, nitrilacarb(1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101(compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX,oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, parathion (615)+TX, permethrin (626)+TX, petroleum oils(628)+TX, phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX,phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon(639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX,polychloroterpenes (traditional name) (1347)+TX, polynactins (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin 1 (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos+TX, selamectin [CCN]+TX, SI-0009 (compound code)+TX,sophamide (1402)+TX, spirodiclofen (738)+TX, spiromesifen (739)+TX,SSI-121 (development code) (1404)+TX, sulfiram [CCN]+TX, sulfluramid(750)+TX, sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code)(757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP(1417)+TX, terbam+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (653)+TX, tetrasul (1425)+TX, thiafenox+TX, thiocarboxime(1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX,thuringiensin [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX,triazophos (820)+TX, triazuron+TX, trichlorfon (824)+TX, trifenofos(1455)+TX, trinactin (653)+TX, vamidothion (847)+TX, vaniliprole [CCN]and YI-5302 (compound code)+TX,an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin [CCN]+TX, emamectin(291)+TX, emamectin benzoate (291)+TX, eprinomectin [CCN]+TX, ivermectin[CCN]+TX, milbemycin oxime [CCN]+TX, moxidectin [CCN]+TX, piperazine[CCN]+TX, selamectin [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen [CCN]+TX, kasugamycin (483)+TX, kasugamycinhydrochloride hydrate (483)+TX, nickel bis(dimethyldithiocarbamate)(IUPAC name) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX,oxolinic acid (606)+TX, oxytetracycline (611)+TX, potassiumhydroxyquinoline sulfate (446)+TX, probenazole (658)+TX, streptomycin(744)+TX, streptomycin sesquisulfate (744)+TX, tecloftalam (766)+TX, andthiomersal [CCN]+TX, a biological agent selected from the group ofsubstances consisting of Adoxophyes orana GV (12)+TX, Agrobacteriumradiobacter (13)+TX, Amblyseius spp. (19)+TX, Anagrapha falcifera NPV(28)+TX, Anagrus atomus (29)+TX, Aphelinus abdominalis (33)+TX, Aphidiuscolemani (34)+TX, Aphidoletes aphidimyza (35)+TX, Autographa californicaNPV (38)+TX, Bacillus firmus (48)+TX, Bacillus sphaericus Neide(scientific name) (49)+TX, Bacillus thuringiensis Berliner (scientificname) (51)+TX, Bacillus thuringiensis subsp. aizawai (scientific name)(51)+TX, Bacillus thuringiensis subsp. israelensis (scientific name)(51)+TX, Bacillus thuringiensis subsp. japonensis (scientific name)(51)+TX, Bacillus thuringiensis subsp. kurstaki (scientific name)(51)+TX, Bacillus thuringiensis subsp. tenebrionis (scientific name)(51)+TX, Beauveria bassiana (53)+TX, Beauveria brongniartii (54)+TX,Chrysoperla carnea (151)+TX, Cryptolaemus montrouzieri (178)+TX, Cydiapomonella GV (191)+TX, Dacnusa sibirica (212)+TX, Diglyphus isaea(254)+TX, Encarsia formosa (scientific name) (293)+TX, Eretmoceruseremicus (300)+TX, Helicoverpa zea NPV (431)+TX, Heterorhabditisbacteriophora and H. megidis (433)+TX, Hippodamia convergens (442)+TX,Leptomastix dactylopii (488)+TX, Macrolophus caliginosus (491)+TX,Mamestra brassicae NPV (494)+TX, Metaphycus helvolus (522)+TX,Metarhizium anisopliae var. acridum (scientific name) (523)+TX,Metarhizium anisopliae var. anisopliae (scientific name) (523)+TX,Neodiprion sertifer NPV and N. lecontei NPV (575)+TX, Orius spp.(596)+TX, Paecilomyces fumosoroseus (613)+TX, Phytoseiulus persimilis(644)+TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus(scientific name) (741)+TX, Steinernema bibionis (742)+TX, Steinernemacarpocapsae (742)+TX, Steinernema feltiae (742)+TX, Steinernema glaseri(742)+TX, Steinernema riobrave (742)+TX, Steinernema riobravis (742)+TX,Steinernema scapterisci (742)+TX, Steinernema spp. (742)+TX,Trichogramma spp. (826)+TX, Typhlodromus occidentalis (844) andVerticillium lecanii (848)+TX,a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir [CCN]+TX, busulfan [CCN]+TX, diflubenzuron(250)+TX, dimatif [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron [CCN]+TX, tepa [CCN]+TX, thiohempa [CCN]+TX,thiotepa [CCN]+TX, tretamine [CCN] and uredepa [CCN]+TX,an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin [CCN]+TX,brevicomin [CCN]+TX, codlelure [CCN]+TX, codlemone (167)+TX, cuelure(179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name)(286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX,10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol [CCN]+TX, frontalin[CCN]+TX, gossyplure (420)+TX, grandlure (421)+TX, grandlurel (421)+TX,grandlurell (421)+TX, grandlure III (421)+TX, grandlure IV (421)+TX,hexalure [CCN]+TX, ipsdienol [CCN]+TX, ipsenol [CCN]+TX, japonilure(481)+TX, lineatin [CCN]+TX, litlure [CCN]+TX, looplure [CCN]+TX,medlure [CCN]+TX, megatomoic acid [CCN]+TX, methyl eugenol (540)+TX,muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name)(588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX,orfralure [CCN]+TX, oryctalure (317)+TX, ostramone [CCN]+TX, siglure[CCN]+TX, sordidin (736)+TX, sulcatol [CCN]+TX, tetradec-11-en-1-ylacetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A(839)+TX, trimedlure B₁ (839)+TX, trimedlure B2 (839)+TX, trimedlure C(839) and trunc-call [CCN]+TX, an insect repellent selected from thegroup of substances consisting of 2-(octylthio)ethanol (IUPAC name)(591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX,dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX,dibutyl succinate (IUPAC name) (1048)+TX, diethyltoluamide [CCN]+TX,dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethyl hexanediol(1137)+TX, hexamide [CCN]+TX, methoquin-butyl (1276)+TX,methylneodecanamide [CCN]+TX, oxamate [CCN] and picaridin [CCN]+TX, aninsecticide selected from the group of substances consisting of1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion [CCN]+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX,acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin [CCN]+TX, allyxycarb (866)+TX, alpha-cypermethrin (202)+TX,alpha-ecdysone [CCN]+TX, aluminium phosphide (640)+TX, amidithion(870)+TX, amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX,amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX,athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compoundcode)+TX, azadirachtin (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (52)+TX, barium hexafluorosilicate[CCN]+TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892)+TX,barthrin [CCN]+TX, Bayer 22/190 (development code) (893)+TX, Bayer 22408(development code) (894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX,bensultap (66)+TX, beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX,bifenthrin (76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenylisomer (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX,bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name) (909)+TX,bistrifluron (83)+TX, borax (86)+TX, brofenvalerate+TX, bromfenvinfos(914)+TX, bromocyclen (918)+TX, bromo-DDT [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben+TX, cadusafos(109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calciumpolysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate(943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide(IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPACname) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap(123)+TX, cartap hydrochloride (123)+TX, cevadine (725)+TX,chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone (963)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin 1(696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin+TX, cismethrin(80)+TX, clocythrin+TX, cloethocarb (999)+TX, closantel [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton [CCN]+TX, crotoxyphos (1010)+TX, crufomate(1011)+TX, cryolite (177)+TX, CS 708 (development code) (1012)+TX,cyanofenphos (1019)+TX, cyanophos (184)+TX, cyanthoate (1020)+TX,cyclethrin [CCN]+TX, cycloprothrin (188)+TX, cyfluthrin (193)+TX,cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX,cyromazine (209)+TX, cythioate [CCN]+TX, d-limonene [CCN]+TX,d-tetramethrin (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX,decarbofuran (1034)+TX, deltamethrin (223)+TX, demephion (1037)+TX,demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX,demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX,demeton-S(1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon(1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diamidafos(1044)+TX, diazinon (227)+TX, dicapthon (1050)+TX, dichlofenthion(1051)+TX, dichlorvos (236)+TX, dicliphos+TX, dicresyl [CCN]+TX,dicrotophos (243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor [CCN]+TX, dimefluthrin [CCN]+TX, dimefox (1081)+TX,dimetan (1085)+TX, dimethoate (262)+TX, dimethrin (1083)+TX,dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex (1089)+TX,dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam (1094)+TX,dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan (1099)+TX,dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion (1102)+TX,disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX, doramectin[CCN]+TX, DSP (1115)+TX, ecdysterone [CCN]+TX, EI 1642 (developmentcode) (1118)+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC(1120)+TX, empenthrin (292)+TX, endosulfan (294)+TX, endothion(1121)+TX, endrin (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane(1124)+TX, eprinomectin [CCN]+TX, esfenvalerate (302)+TX, etaphos[CCN]+TX, ethiofencarb (308)+TX, ethion (309)+TX, ethiprole (310)+TX,ethoate-methyl (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPACname) [CCN]+TX, ethyl-DDD (1056)+TX, ethylene dibromide (316)+TX,ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX,etofenprox (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, famphur(323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos(1148)+TX, fenethacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion(335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb(340)+TX, fenpirithrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor(1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (473)+TX, isodrin (1235)+TX,isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX,ivermectin [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX,jodfenphos (1248)+TX, juvenile hormone I [CCN]+TX, juvenile hormone II[CCN]+TX, juvenile hormone III [CCN]+TX, kelevan (1249)+TX, kinoprene(484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX,lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos(1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenylmethylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name)(640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX,mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan(1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX,metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (519)+TX,metam-sodium (519)+TX, methacrifos (1266)+TX, methamidophos (527)+TX,methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268)+TX,methidathion (529)+TX, methiocarb (530)+TX, methocrotophos (1273)+TX,methomyl (531)+TX, methoprene (532)+TX, methoquin-butyl (1276)+TX,methothrin (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX,methyl bromide (537)+TX, methyl isothiocyanate (543)+TX,methylchloroform [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime[CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, monocrotophos (561)+TX,morphothion (1300)+TX, moxidectin [CCN]+TX, naftalofos [CCN]+TX, naled(567)+TX, naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O, O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron [CCN]+TX, pentachlorophenol(623)+TX, pentachlorophenyl laurate (IUPAC name) (623)+TX, permethrin(626)+TX, petroleum oils (628)+TX, PH 60-38 (development code)(1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate(631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX,phosmet (638)+TX, phosnichlor (1339)+TX, phosphamidon (639)+TX,phosphine (IUPAC name) (640)+TX, phoxim (642)+TX, phoxim-methyl(1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX, pirimiphos-ethyl(1345)+TX, pirimiphos-methyl (652)+TX, polychlorodicyclopentadieneisomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name)(1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX,prallethrin (655)+TX, precocene I [CCN]+TX, precocene II [CCN]+TX,precocene Ill [CCN]+TX, primidophos (1349)+TX, profenofos (662)+TX,profluthrin [CCN]+TX, promacyl (1354)+TX, promecarb (1355)+TX, propaphos(1356)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothiofos (686)+TX, prothoate (1362)+TX, protrifenbute[CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrazophos(693)+TX, pyresmethrin (1367)+TX, pyrethrin 1 (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX,pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX,pyriproxyfen (708)+TX, quassia [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide [CCN]+TX, resmethrin(719)+TX, rotenone (722)+TX, RU 15525 (development code) (723)+TX, RU25475 (development code) (1386)+TX, ryania (1387)+TX, ryanodine(traditional name) (1387)+TX, sabadilla (725)+TX, schradan (1389)+TX,sebufos+TX, selamectin [CCN]+TX, SI-0009 (compound code)+TX, SI-0205(compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compoundcode)+TX, silafluofen (728)+TX, SN 72129 (development code) (1397)+TX,sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoride(IUPAC/Chemical Abstracts name) (1399)+TX, sodium hexafluorosilicate(1400)+TX, sodium pentachlorophenoxide (623)+TX, sodium selenate (IUPACname) (1401)+TX, sodium thiocyanate [CCN]+TX, sophamide (1402)+TX,spinosad (737)+TX, spiromesifen (739)+TX, spirotetrmat (CCN)+TX,sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfluramid (750)+TX,sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulprofos (1408)+TX, taroils (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE(1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos(764)+TX, teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos(770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam+TX, terbufos(773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos (777)+TX,tetramethrin (787)+TX, theta-cypermethrin (204)+TX, thiacloprid(791)+TX, thiafenox+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX,thiocarboxime (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogenoxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon(801)+TX, thionazin (1434)+TX, thiosultap (803)+TX, thiosultap-sodium(803)+TX, thuringiensin [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin(812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, triamiphos(1441)+TX, triazamate (818)+TX, triazophos (820)+TX, triazuron+TX,trichlorfon (824)+TX, trichlormetaphos-3 [CCN]+TX, trichloronat(1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX, trimethacarb(840)+TX, triprene (1459)+TX, vamidothion (847)+TX, vaniliprole[CCN]+TX, veratridine (725)+TX, veratrine (725)+TX, XMC (853)+TX,xylylcarb (854)+TX, YI-5302 (compound code)+TX, zeta-cypermethrin(205)+TX, zetamethrin+TX, zinc phosphide (640)+TX, zolaprofos (1469) andZXI 8901 (development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX,a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX, a nematicide selected from the group of substancesconsisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane(IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane(IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene(233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/ChemicalAbstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPACname) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid(IUPAC name) (1286)+TX, 6-isopentenylaminopurine (210)+TX, abamectin(1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb (16)+TX,aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz [CCN]+TX,benomyl (62)+TX, butylpyridaben+TX, cadusafos (109)+TX, carbofuran(118)+TX, carbon disulfide (945)+TX, carbosulfan (119)+TX, chloropicrin(141)+TX, chlorpyrifos (145)+TX, cloethocarb (999)+TX, cytokinins(210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos(1044)+TX, dichlofenthion (1051)+TX, dicliphos+TX, dimethoate (262)+TX,doramectin [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX,eprinomectin [CCN]+TX, ethoprophos (312)+TX, ethylene dibromide(316)+TX, fenamiphos (326)+TX, fenpyrad+TX, fensulfothion (1158)+TX,fosthiazate (408)+TX, fosthietan (1196)+TX, furfural [CCN]+TX, GY-81(development code) (423)+TX, heterophos [CCN]+TX, iodomethane (IUPACname) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX, ivermectin[CCN]+TX, kinetin (210)+TX, mecarphon (1258)+TX, metam (519)+TX,metam-potassium (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime [CCN]+TX,moxidectin [CCN]+TX, Myrothecium verrucaria composition (565)+TX, NC-184(compound code)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon(639)+TX, phosphocarb [CCN]+TX, sebufos+TX, selamectin [CCN]+TX,spinosad (737)+TX, terbam+TX, terbufos (773)+TX, tetrachlorothiophene(IUPAC/Chemical Abstracts name) (1422)+TX, thiafenox+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron+TX, xylenols [CCN]+TX, YI-5302(compound code) and zeatin (210)+TX, fluensulfone [318290-98-1]+TX, anitrification inhibitor selected from the group of substances consistingof potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (720)+TX, a rodenticide selected fromthe group of substances consisting of 2-isovalerylindan-1,3-dione (IUPACname) (1246)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name)(748)+TX, alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX,antu (880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (850)+TX, coumachlor(1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX, crimidine(1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, diphacinone(273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX, fluoroacetamide(379)+TX, flupropadine (1183)+TX, flupropadine hydrochloride (1183)+TX,gamma-HCH (430)+TX, HCH (430)+TX, hydrogen cyanide (444)+TX, iodomethane(IUPAC name) (542)+TX, lindane (430)+TX, magnesium phosphide (IUPACname) (640)+TX, methyl bromide (537)+TX, norbormide (1318)+TX,phosacetim (1336)+TX, phosphine (IUPAC name) (640)+TX, phosphorus[CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron(1371)+TX, scilliroside (1390)+TX, sodium arsenite [CCN]+TX, sodiumcyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX,thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (324)+TX, MB-599 (development code) (498)+TX,MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX,piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code)(724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,a virucide selected from the group of substances consisting of imanin[CCN] and ribavirin [CCN]+TX,a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,and biologically active compounds selected from the group consisting ofazaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole[116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole[119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole[106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole[136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol[76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX,imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate[101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole[178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX,propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX,tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX,triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine[2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX,azoxystrobin [131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX,enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX,fluoxastrobin [361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX,metominostrobin [133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX,orysastrobin [248593-16-0]+TX, picoxystrobin [117428-22-5]+TX,pyraclostrobin [175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb[8018-01-7]+TX, maneb [12427-38-2]+TX, metiram [9006-42-2]+TX, propineb[12071-83-9]+TX, thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram[137-30-4]+TX, captafol [2425-06-1]+TX, captan [133-06-2]+TX,dichlofluanid [1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet[133-07-3]+TX, tolylfluanid [731-27-1]+TX, bordeaux mixture[8011-63-0]+TX, copperhydroxid [20427-59-2]+TX, copperoxychlorid[1332-40-7]+TX, coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX,mancopper [53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap[131-72-6]+TX, nitrothal-isopropyl [10552-74-6]+TX, edifenphos[17109-49-8]+TX, iprobenphos [26087-47-8]+TX, isoprothiolane[50512-35-1]+TX, phosdiphen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX,tolclofos-methyl [57018-04-9]+TX, acibenzo-lar-S-methyl[135158-54-2]+TX, anilazine [101-05-3]+TX, benthiavalicarb[413615-35-7]+TX, blasticidin-S [2079-00-7]+TX, chinomethionat[2439-01-2]+TX, chloroneb [2675-77-6]+TX, chlorothalonil [1897-45-6]+TX,cyflufenamid [180409-60-3]+TX, cymoxanil [57966-95-7]+TX, dichlone[117-80-6]+TX, diclocymet [139920-32-4]+TX, diclomezine [62865-36-5]+TX,dicloran [99-30-9]+TX, diethofencarb [87130-20-9]+TX, dimethomorph[110488-70-5]+TX, SYP-LI90 (Flumorph) [211867-47-9]+TX, dithianon[3347-22-6]+TX, ethaboxam [162650-77-3]+TX, etridiazole [2593-15-9]+TX,famoxadone [131807-57-3]+TX, fenamidone [161326-34-7]+TX, fenoxanil[115852-48-7]+TX, fentin [668-34-8]+TX, ferimzone [89269-64-7]+TX,fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide[106917-52-6]+TX, fenhexamid [126833-17-8]+TX, fosetyl-aluminium[39148-24-8]+TX, hymexazol [10004-44-1]+TX, iprovalicarb[140923-17-7]+TX, IKF-916 (Cyazofamid) [120116-88-3]+TX, kasugamycin[6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, metrafenone[220899-03-6]+TX, pencycuron [66063-05-6]+TX, phthalide [27355-22-2]+TX,polyoxins [11113-80-7]+TX, probenazole [27605-76-1]+TX, propamocarb[25606-41-1]+TX, proquinazid [189278-12-4]+TX, pyroquilon[57369-32-1]+TX, quinoxyfen [124495-18-7]+TX, quintozene [82-68-8]+TX,sulfur [7704-34-9]+TX, tiadinil [223580-51-6]+TX, triazoxide[72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine[26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (RH7281)[156052-68-5]+TX, mandipropamid [374726-62-2]+TX, isopyrazam[881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-difluoromethyl-l1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(dislosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a, 12b-trimethyl-1-oxo-9-(3-pyridinyl)-2H, 11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX and1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX, lancotrione [1486617-21-3]+TX, florpyrauxifen[943832-81-3]]+TX, ipfentrifluconazole[1417782-08-1]+TX,mefentrifluconazole [1417782-03-6]+TX, quinofumelin [861647-84-9]+TX,chloroprallethrin [399572-87-3]+TX, cyhalodiamide [1262605-53-7]]+TX,fluazaindolizine [1254304-22-7]+TX, fluxametamide [928783-29-3]+TX,epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin[1065124-65-3]+TX, pydiflumetofen [1228284-64-7]+TX, kappa-bifenthrin[439680-76-9]+TX, broflanilide [1207727-04-5]+TX, dicloromezotiaz[1263629-39-5]+TX, dipymetitrone [16114-35-5]+TX, pyraziflumid[942515-63-1]+TX, kappa-tefluthrin [391634-71-2]+TX, fenpicoxamid[517875-34-2]+TX; fluindapyr [1383809-87-7]+TX; alpha-bromadiolone[28772-56-7]+TX; flupyrimin [1689566-03-7]+TX; benzpyrimoxan[1449021-97-9]+TX; acynonapyr [1332838-17-1]+TX; inpyrfluxam[1352994-67-2]+TX, isoflucypram [1255734-28-1]+TX; rescalure[64309-03-1]+TX; aminopyrifen [1531626-08-0]+TX; tyclopyrazoflor[1477919-27-9]+TX; and spiropidion [1229023-00-0]+TX; and microbialsincluding: Acinetobacter iwoffii+TX, Acremonium alternatum+TX+TX,Acremonium cephalosporium+TX+TX, Acremonium diospyri+TX, Acremoniumobclavatum+TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®)+TX,Agrobacterium radiobacter strain K84 (Galltrol-A®)+TX, Alternariaalternate+TX, Alternaria cassia+TX, Alternaria destruens (Smolder®)+TX,Ampelomyces quisqualis (AQ10®)+TX, Aspergillus flavus AF36 (AF36®)+TX,Aspergillus flavus NRRL 21882 (Aflaguard®)+TX, Aspergillus spp.+TX,Aureobasidium pullulans+TX, Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX,Azotobacter+TX, Azotobacter chroocuccum (Azotomeal®)+TX, Azotobactercysts (Bionatural Blooming Blossoms®)+TX, Bacillus amyloliquefaciens+TX,Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacilluschitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2(Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086(EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus(BioSafe®, BioNem-WP®, VOTiVO®)+TX, Bacillus firmus strain 1-1582+TX,Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX,Bacillus mycoides strain AQ726+TX, Bacillus papillae (Milky SporePowder®)+TX, Bacillus pumilus spp.+TX, Bacillus pumilus strain GB34(Yield Shield®)+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilusstrain QST 2808 (Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus(VectoLex®)+TX, Bacillus spp.+TX, Bacillus spp. strain AQ175+TX,Bacillus spp. strain AQ177+TX, Bacillus spp. strain AQ178+TX, Bacillussubtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX,Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strainAQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strainQST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var.amyloliquefaciens strain FZB24 (Taegro®+TX, Rhizopro®)+TX, Bacillusthuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillusthuringiensis aizawai GC 91 (Agree®)+TX, Bacillus thuringiensisisraelensis (BMP123®+TX, Aquabac®+TX, VectoBac®)+TX, Bacillusthuringiensis kurstaki (Javelin®+TX, Deliver®+TX, CryMax®+TX,Bonide®+TX, Scutella WP®+TX, Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX,Biobit®+TX, Foray®)+TX, Bacillus thuringiensis kurstaki BMP 123(Baritone®)+TX, Bacillus thuringiensis kurstaki HD-1(Bioprotec-CAF/3P®)+TX, Bacillus thuringiensis strain BD#32+TX, Bacillusthuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai(XenTari®+TX, DiPel®)+TX, bacteria spp. (GROWMEND®+TX, GROWSWEET®+TX,Shootup®)+TX, bacteriophage of Clavipacter michiganensis(AgriPhage®)+TX, Bakflor®+TX, Beauveria bassiana (Beaugenic®+TX,Brocaril WP®)+TX, Beauveria bassiana GHA (Mycotrol ES®+TX, MycotrolO®+TX, BotaniGuard®)+TX, Beauveria brongniartii (Engerlingspilz®+TX,Schweizer Beauveria®+TX, Melocont®)+TX, Beauveria spp.+TX, Botrytiscineria+TX, Bradyrhizobium japonicum (TerraMax®)+TX, Brevibacillusbrevis+TX, Bacillus thuringiensis tenebrionis (Novodor®)+TX,BtBooster+TX, Burkholderia cepacia (Deny®+TX, Intercept®+TX, BlueCircle®)+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX,Burkholderia spp.+TX, Canadian thistle fungus (CBH CanadianBioherbicide®)+TX, Candida butyri+TX, Candida famata+TX, Candidafructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candidamelibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX,Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX,Candida saitoana (Bio-Coat®+TX, Biocure®)+TX, Candida sake+TX, Candidaspp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonasflavigena+TX, Chaetomium cochliodes (Nova-Cide®)+TX, Chaetomium globosum(Nova-Cide®)+TX, Chromobacterium subtsugae strain PRAA4-1T(Grandevo®)+TX, Cladosporium cladosporioides+TX, Cladosporiumoxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX,Cladosporium tenuissimum+TX, Clonostachys rosea (EndoFine®)+TX,Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans WG®)+TX,Coniothyrium spp.+TX, Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcushumicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcuslaurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex®)+TX,Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX,Cydia pomonella granulovirus (Madex®+TX, Madex Plus®+TX, MadexMax/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX,Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslerahawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX,Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccumpurpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusariumacuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum(Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX,Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX,Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX,Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX,Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillustrueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibriovariabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigeranucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclearpolyhedrosis virus (Gemstar®)+TX, Isoflavone-formononetin(Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidiumgiganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX,Lecanicillium muscarium (Vertikil®)+TX, Lymantria Disparnucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX,Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhiziumanisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX,Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX,Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp.(AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strainAARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97(Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus(PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX,Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacilluspolymyxa+TX, Pantoea agglomerans (BlightBan C₉-1®)+TX, Pantoea spp.+TX,Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicilliumaurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX,Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicilliumgriseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX,Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX,phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthoracryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX,Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX,Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens(Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonaschlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonasfluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX,Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae(Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens(Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX,Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythiumparoecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX,Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia(Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strainAQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX,Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX,Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomycescerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotiniaminor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX,Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX,Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX,Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus(Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonasmaltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomycesalbaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX,Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX,Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108(ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX,Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX,Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX,Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai(Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShieldHC®+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39(Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX,Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX,Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX,Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerlyGliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX,Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporonpullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichotheciumroseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhizastrain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii(Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementarymicronutrients (Natural II®)+TX, various fungi (MillenniumMicrobes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii(Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillusmarismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX,Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; andPlant extracts including: pine oil (Retenol®)+TX, azadirachtin (PlasmaNeem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR(Neemazad®, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX,Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemumextract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentialsoils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermintand thyme oil (Garden insect Killer®)+TX, Glycinebetaine(Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neemoil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX,oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX,pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis(Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plantextract (Soleo®)+TX, soybean oil (Ortho Ecosense®)+TX, tea tree oil(Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixtureof rosemary sesame pepermint thyme and cinnamon extracts (EF 300®)+TX,mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixtureof clove pepermint garlic oil and mint (Soil Shot®)+TX, kaolin(Screen®)+TX, storage glucam of brown algae (Laminarin®)+TX; andpheromones including: blackheaded fireworm pheromone (3M SprayableBlackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramountdispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3MMEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC-LRSprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar PremiumFly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit mothsprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX,Tomato Pinworm Pheromone (3M Sprayable Pheromone®)+TX, Entostat powder(extract from palm tree) (Exosex CM®)+TX, Tetradecatrienyl acetate+TX,13-Hexadecatrienal+TX, (E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX,2-Methyl-1-butanol+TX, Calcium acetate+TX, Scenturion®+TX, Biolure®+TX,Check-Mate®+TX, Lavandulyl senecioate; andMacrobials including: Aphelinus abdominalis+TX, Aphidius ervi(Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata(Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata(Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX,Amblyseius andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseiuscalifornicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris(Thripex®+TX, Bugline Cucumeris®)+TX, Amblyseius fallacis(Fallacis®)+TX, Amblyseius swirskii (Bugline Swirskii®+TX,Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitushesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyruskamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX,Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocorisnemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX,Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX,Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae(Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletesaphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytismelinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX,Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombusterrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX,Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperlacarnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilusingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichusphyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX,Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX,Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX,Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalusnipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX,Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX,Delphastus pusillus+TX, Diachasmimorpha krausii+TX, DiachasmimorphaIongicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX,Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX,Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX,Encarsia citrina+TX, Encarsia formosa (Encarsia Max®+TX, Encarline®+TX,En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsiaguadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus(Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX,Eretmocerus eremicus (Ercal®+TX, Eretline E®)+TX, Eretmocerus eremicus(Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX,Eretline M®)+TX, Eretmocerus siphonini+TX, Exochomusquadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiellaacarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX,Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis(Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX,Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX,Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora(NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®+TX,Larvanem®+TX, B-Green®+TX, NemAttack®+TX, Nematop®)+TX, Heterorhabditismegidis (Nemasys H®+TX, BioNem H®+TX, Exhibitline Hm®+TX,Larvanem-M®)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer(Aculeifer-System®+TX, Entomite-A®)+TX, Hypoaspis miles (Hypoline M®+TX,Entomite-M®)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX,Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastixdactylopii (Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX,Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebustestaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline C®+TX,Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycuslounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterysflavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX,Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiuluscucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis(NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Oriusinsidiosus (Thripor-I®+TX, Oriline I®)+TX, Orius laevigatus(Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline M®)+TX, Oriusstrigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobiusfoveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX,Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiuluspersimilis (Spidex®+TX, Phytoline P®)+TX, Podisus maculiventris(Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX,Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastixmexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX,Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX,Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae(Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX,BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernemafeltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX,Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline Sf®+TX,Scia-Rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNemL®+TX, Exhibitline Srb®)+TX, Steinernema riobrave (BioVector®+TX,BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernemaspp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethoruspunctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichussetifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogrammabrassicae (Tricholine B®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX,Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogrammaostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX,Xanthopimpla stemmator; andother biologicals including: abscisic acid+TX, bioSea®+TX,Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichumgloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps(Trapline D®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT GoldCST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline Y®)+TX,Gallex®+TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate(Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap(Trapline F®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris(Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap(Thripline Ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassiumsalts of fatty acids (Sanova®)+TX, potassium silicate solution(Sil-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX,SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore OrganicGrasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, RebellAmarillo®)+TX and Traps (Takitrapline y+B®)+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright © 1995-2004]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used. “CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom Table 1 and A with active ingredients described above comprises acompound selected from Table 1 and A and an active ingredient asdescribed above preferably in a mixing ratio of from 100:1 to 1:6000,especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to1:20, even more especially from 10:1 to 1:10, very especially from 5:1and 1:5, special preference being given to a ratio of from 2:1 to 1:2,and a ratio of from 4:1 to 2:1 being likewise preferred, above all in aratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750.Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Table 1and A and one or more active ingredients as described above can beapplied, for example, in a single “ready-mix” form, in a combined spraymixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromTable 1 and A and the active ingredients as described above is notessential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also besuitable for the protection of plant propagation material, for exampleseeds, such as fruit, tubers or kernels, or nursery plants, againstpests of the abovementioned type. The propagation material can betreated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound of formula I. The term “coated or treated withand/or containing” generally signifies that the active ingredient is forthe most part on the surface of the seed at the time of application,although a greater or lesser part of the ingredient may penetrate intothe seed material, depending on the method of application. When the saidseed product is (re)planted, it may absorb the active ingredient. In anembodiment, the present invention makes available a plant propagationmaterial adhered thereto with a compound of formula (I). Further, it ishereby made available, a composition comprising a plant propagationmaterial treated with a compound of formula (I).

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundformula (I) can be carried out by any known methods, such as spraying orby dusting the seeds before sowing or during the sowing/planting of theseeds.

Biological Examples Example B1: Activity Against Diabrotica balteata(Corn Root Worm)

Maize sprouts placed onto an agar layer in 24-well microtiter plateswere treated with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions by spraying. After drying, the plates were infested withL2 larvae (6 to 10 per well). The samples were assessed for mortalityand growth inhibition in comparison to untreated samples 4 days afterinfestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: A1, A2, A3, A4, A5, A6, A7, A8, A9, A12, A13, A14, A15,A16, A17, A19, A21, A22, A23, A24 and A25.

Example B2: Activity Against Euschistus heros (Neotropical Brown StinkBug)

Soybean leaves on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaves were infested with N2 nymphs. The samples wereassessed for mortality and growth inhibition in comparison to untreatedsamples 5 days after infestation.

The following compound gave an effect of at least 80% in at least one ofthe two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: A2, A3, A4, A5, A6, A7, A8, A9, A12, A13, A14, A15,A16, A17, A19, A21, A22, A23, A24 and A25.

Example B3: Activity Against Myzus persicae (Green Peach Aphid):Feeding/Contact Activity

Sunflower leaf discs were placed onto agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10′000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: A1, A2, A3, A4, A5, A6, A7, A8, A9, A12,A13, A14, A15, A16, A17, A19, A21 and A22.

Example B4: Activity Against Myzus persicae (Green Peach Aphid):Systemic Activity

Roots of pea seedlings infested with an aphid population of mixed ageswere placed directly into aqueous test solutions prepared from 10′000DMSO stock solutions. The samples were assessed for mortality 6 daysafter placing seedlings into test solutions.

The following compound resulted in at least 80% mortality at a test rateof 24 ppm: A2, A3, A4, A5, A6, A7, A8, A9, A12, A13, A14, A15, A17 andA22.

Example B5: Activity Against Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10′000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality and growthinhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: A1, A2, A3, A4, A5, A6, A7, A8, A9, A12, A13, A14, A15,A16, A17, A19, A21, A22, A23 and A24.

Example B6: Activity Against Spodoptera littoralis (Egyptian Cotton LeafWorm)

Cotton leaf discs were placed onto agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality, anti-feeding effect,and growth inhibition in comparison to untreated samples 3 days afterinfestation. Control of Spodoptera littoralis by a test sample is givenwhen at least one of the categories mortality, anti-feedant effect, andgrowth inhibition is higher than the untreated sample.

The following compounds resulted in at least 80% control at anapplication rate of 200 ppm: A1, A2, A3, A4, A5, A6, A7, A8, A9, A12,A13, A14, A16, A17, A19, A21, A22, and A23.

Example B7: Activity Against Spodoptera littoralis (Egyptian Cotton LeafWorm)

Test compounds were applied by pipette from 10′000 ppm DMSO stocksolutions into 24-well plates and mixed with agar. Lettuce seeds wereplaced onto the agar and the multi well plate was closed by anotherplate which contained also agar. After 7 days the compound was absorbedby the roots and the lettuce grew into the lid plate. The lettuce leaveswere then cut off into the lid plate. Spodoptera eggs were pipettedthrough a plastic stencil onto a humid gel blotting paper and the lidplate was closed with it. The samples were assessed for mortality,anti-feedant effect and growth inhibition in comparison to untreatedsamples 6 days after infestation.

The following compound gave an effect of at least 80% in at least one ofthe three categories (mortality, anti-feeding, or growth inhibition) ata test rate of 12.5 ppm: A2.

Example B8: Activity Against Bemisia tabaci (Cotton White Fly)

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10′000 ppm DMSO stocksolutions. After drying the leaf discs were infested with adult whiteflies. The samples were checked for mortality 6 days after incubation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: A3, A4, A8, A9, A12, A13, A14, A15 and A17.

Example B9: Activity Against Tetranychus urticae (Two-Spotted SpiderMite)

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: A3 and A8, and A9.

Example B10: Comparison of the Insecticidal Activity of Compound A2According to this Invention with the Structurally Closest Compound fromthe State of the Art

The pesticidal activity of compound A2 according to the preparatoryexamples and of compound A17 from WO 2016/7023954 against Spodopteralittoralis (test Example B6 above), Plutella xylostella (Example B5),Diabrotica balteata (Example B1), Myzus persicae (feeding/contact,Example B3) and Myzus persicae (systemic, Example B4) is summarized inTable B10:

TABLE B10 Concentration Compound (ppm) Insect Mortality (%) A2

(present invention) 12.5 12.5 50   50      1.5 Spodoptera littoralisPlutella xylostella Diabrotica balteata Myzus persicae (feeding/contact)Myzus persicae (systemic)  80  80 100 100    80 A17, known from WO2016/023954

(state of the art) 12.5 12.5 50   50      1.5 Spodoptera littoralisPlutella xylostella Diabrotica balteata Myzus persicae (feeding/contact)Myzus persicae (systemic)  0  0  0  50    0

Table B10 shows that compound A2 according to the invention exhibits asubstantially better insecticidal action on Spodoptera littoralis,Plutella xylostella, Diabrotica balteata and Myzus persicae(feeding/contact and systemic activity) than the compound from the stateof the art at the tested application rates. This enhanced effect was notto be expected on the basis of the structural similarity of thesecompounds.

Example B11: Activity Against Frankliniella occidentalis (Western FlowerThrips)

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10′000 DMSO stocksolutions. After drying the leaf discs were infested with aFrankliniella population of mixed ages. The samples were assessed formortality 7 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: A12.

The invention claimed is:
 1. A compound of formula Z-1

R₂ is CF₃; R₄ is unsubstituted alkyl; X₁ is halogen or azido; Ry ishydrogen or t-butyloxycarbonyl; and Rz is C₁-C₄alkyl.
 2. The compound offormula Z-1 according to claim 1, wherein R₄ is C₁-C₆alkyl.
 3. Thecompound of formula Z-1 according to claim 2, wherein R₄ is CH₃.
 4. Thecompound of formula Z-1 according to claim 3, wherein X₁ is azide. 5.The compound of formula Z-1 according to claim 4, wherein Rz is CH₃. 6.The compound of formula Z-1 according to claim 3, wherein X₁ is halogen.7. The compound of formula Z-1 according to claim 6, wherein Rz is CH₃.